Substituted pyridines/pyrimidines, their preparation, and their use as pesticides

ABSTRACT

The present invention relates to novel substituted pyridines/pyrimidines of the formula I                    
     where A is CH or N; X is NH, oxygen or S(O) q  where q is 0, 1 or 2; Y is a direct bond or CH 2 ; Z is oxygen, NR 7  or S(O) m  is 0, 1 or 2, and the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are as defined in the description, to processes for their preparation, and to their use as pesticides, fungicides, ovicides or as veterinary medicaments.

The invention relates to novel substituted pyridines/pyrimidines, toprocesses for their preparation and to their use as pesticides,fungicides and ovicides.

It has already been disclosed that certain cycloalkylamino- and-alkoxy-heterocycles have a fungicidal, acaricidal and insectidal action(U.S. Pat. No. 5,571,825). However, the biological activity of thesecompound is not satisfactory in all respects, in particular when lowrates and concentrations are applied.

There have been found novel substituted pyridines/pyrimidines of theformula I

where the radicals and groups are as defined below and which are highlysuitable for controlling animal pests such as insects, arachnids,nematodes, helminths and mollusks and their eggs, for controlling endo-and ectoparasites in the veterinary medicine sector and for controllingharmful fungi while having good plant tolerance and favorable toxicityto warm-blooded species.

The invention therefore relates to compounds of the formula I in which

R¹ is hydrogen, halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl or(C₃-C₅)-cycloalkyl;

R² and R³ independently of one another are hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-haloalkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl,(C₂-C₄)-alkynyl, (C₂-C₄)-haloalkynyl,tri-(C₁-C₄)-alkylsilyl-(C₂-C₄)-alkynyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,(C₁-C₄)-haloalkoxy-(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-haloalkyl,(C₁-C₄)-haloalkoxy-(C₁-C₄)-haloalkyl, halogen, hydroxyl,(C₁-C₄)-hydroxyalkyl, (C₁-C₄)-alkanoyl, (C₁-C₄)-alkanoyl-(C₁-C₄)-alkyl,(C₂-C₄)-haloalkanoyl, (C₃-C₅)-cycloalkyl, (C₃-C₅)-halocycloalkyl,(C₄-C₅)-cyCloalkenyl, (C₄-C₅)-halocycloalkenyl, (C₃-C₅)cycloalkoxy,cyano, cyan-(C₁-C₄)-alkyl, nitro, nitro-(C₁-C₄)-alkyl, thiocyano,thiocyano-(C₁-C₄)-alkyl, (C₁-C₄)-alkoxycarbonyl,(C₁-C₄)-alkoxycarbonyl-(C₁-C₄)-alkyl, (C₁-C₄)-haloalkoxycarbonyl,(C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,(C₁-C₄)-alkylthio-C₁-C₄)-alkyl, (C₁-C₄)-haloalkylthio-(C₁-C₄)-alkyl,(C₁-C₄)-alkylthio-(C₁-C₄)-haloalkyl, (C₁-C₄)-alkylsulfinyl,(C₁-C₄)-haloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl,(C₁-c₄)-haloalkylsulfonyl; or

R² and R³ together with the carbon atoms to which they are bonded forman unsaturated 5- or 6-membered carbocyclic ring which, if it is a5-membered ring, can contain an oxygen or sulfur atom instead of CH₂ orwhich, if it is a 6-membered ring, can contain one or two nitrogen atomsinstead of one or two CH units and which is optionally substituted by 1,2 or 3 identical or different radicals and these radicals being(C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, preferably trifluoromethyl, halogen,(C₁-C₄)-alkoxy or (C₁-C₄)-haloalkoxy; or

R² and R³ together with the carbon atoms to which they are bonded form asaturated 5-, 6- or 7-membered carbocyclic ring which can contain oxygenand/or sulfur instead of one or two CH₂-groups and which is optionallysubstituted by 1, 2 or 3 (C₁-C₄)-alkyl groups;

A is CH or N;

X is NH, oxygen or S(O)_(q) where q=0, 1 or 2;

Y is a direct bond or CH₂;

Z is oxygen, NR⁷, S(O)_(m) where m=0, 1 or 2;

R⁴,R⁵ and W-R⁶ are substituents of the heteroaliphatic ring system,where

R⁴ and R⁵ independently of one another are hydrogen, halogen, cyano,(C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl,(C₂-C₄)-alkynyl, (C₂-C₄)-haloalkynyl, (C₃-C₆)-cycloalkyl,(C₄-C₆)-cycloalkenyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy,(C₁-C₄)-alkanoyloxy, (C₁-C₄)-haloalkanoyloxy, (C₁-C₄)-alkylthio or(C₁-C₄)-haloalkylthio;

W is a direct bond, oxygen, —NR¹²—, —CO—, —COO—, CONR¹²—, sulfur, —C=N—,—C=N—O— or —NR¹²O—;

R⁶ is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl andit being possible for one or more, preferably up to three, non-adjacentsaturated carbon units in the last-mentioned 5 radicals to be replacedby a carbonyl group or by hetero atom units such as oxygen, S(O)_(x)where x=0, 1 or 2, NR¹³ or SiR¹⁴R¹⁵, and it being possible for theselast-mentioned 5 radicals, with or without the abovementionedvariations, optionally to be substituted by one or more, preferably upto three, in the case of fluorine up to the maximum number of, identicalor different radicals D¹R¹⁶, or

R⁶ can be aryl or heterocyclyl, it being possible for these two radicalsto be unsubstituted or substituted by up to three, in the case offluorine also up to the maximum number of, identical or differentradicals D²R¹⁷, or

R⁴ and R⁶ together form a three- to eight-membered ring system which islinked spirocyclically to the ring system which contains the heteroatoms Y and Z and in which one or two CH₂ groups, preferably one CH₂group, can be replaced by hetero atom units such as oxygen, S(O)_(n)where n=0, 1 or 2, or NR¹⁸,

where

R⁷ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₂-C₄)-alkenyl,(C₂-C₄)-haloalkenyl, (C₂-C₄)-alkynyl, (C₂-C₄)-haloalkynyl,(C₁-C₄)-alkoxy, (C₁-C₄)-alkanoyl, (C₂-C₄)-haloalkanoyl,(C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, (C₁-C₄)-alkylthio-(C₁-C₄)-alkyl,(C₁-C₄)-alkoxycarbonyl, (C₁-C₄)-alkylsulfonyl,(C₁-C₄)-haloalkylsulfonyl, phenylcarbonyl, phenyl-(C₁-C₄)-alkyl or, if Ais N, also phenyl, it being possible for the last-mentioned 3 radicalsto be unsubstituted or to be substituted by up to three, in the case offluorine also up to the maximum number of, identical or differentsubstituents R¹¹, or

R⁷ is CONR⁸R⁹, in which

R⁸ and R⁹ independently of one another are hydrogen, (C₁-C₄)-alkyl orphenyl, it being possible for the phenyl group to be unsubstituted orsubstituted by up to three, in the case of fluorine also up to themaximum number of, identical or different substituents R¹⁰, and

R¹⁰ and R¹¹ independently of one another can be (C₁-C₄)-alkyl,(C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthioor halogen;

R¹² is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkanoyl or (C₃-C₅)-cycloalkyl;

R¹³ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or (C₁-C₄)-alkanoyl;

R¹⁴ and R¹⁵ independently of one another are (C₁-C₄)-alkyl, preferablymethyl;

R¹⁸ is hydrogen, alkyl, alkanoyl, alkoxy, benzoyl, aryl or heteroaryl,it being possible for the last-mentioned 3 radicals to be unsubstitutedor to be provided with up to three, in the case of fluorine also up tothe maximum number of, identical or different substituents R¹⁹;

R¹⁹ can be (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkoxy, cyano, nitro or halogen, and the ring system formedby R⁴ and R⁶ can be unsubstituted or provided with up to threesubstituents, but preferably one substituent, D³R²⁰, or the ring systemformed by R⁴ and R⁶ together with a further benzene ring or cydohexanering forms a fused ring system, preferably the indane,1,2,3,4-tetrahydronaphthalene, decalin or benzocycloheptane system, andthe benzene ring in these fused systems can be unsubstituted or providedwith up to three, in the case of fluorine also up to the maximum numberof, identical or different substituents D⁴R²¹, where

D¹, D^(2,) D³ and D⁴ are in each case independent of one another and area direct bond, oxygen, S(O)_(k), SO₂O, OSO₂, CO, OCO, COO, SO₂NR²²,NR²²SO₂, NR²²O, ONR²², NR²², NR²²CO, CONR²² or SiR²³R²⁴, where k is 0, 1or 2; and

R¹⁶, R¹⁷, R²⁰ and R²¹ in each case independently of one another arehydrogen, cyano, nitro, halogen, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl,(C₂-C₈)-alkenyl, (C₂-C₈)-haloalkenyl, (C₂-C₈)alkynyl,(C₂-C₈)-haloalkynyl, (C₁-C₈)-alkoxy (C₁-C₄)-alkyl,(C₁-C₈)-haloalkoxy(C₁-C₄)-alkyl, (C₁-C₈)-alkylthio(C₁-C₄)-alkyl,(C₁-C₈)-haloalkylthio(C₁-C₄)-alkyl, (C₃-C₈)-cycloalkyl,(C₄-C₈)cycloalkenyl, (C₃-C₈)-cycloalkyl-(C₁-C₄)-alkyl,(C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkyl, aryl, heterocyclyl,aryl-(C₁-C₄)-alkyl or heterocyclyl-(C₁-C₄)-alkyl, it being possible forthe cycloaliphatic, aromatic or heterocyclic ring systems in thelast-mentioned 8 radicals to be unsubstituted or to be provided by up tothree, in the case of fluorine also up to the maximum number of,identical or different substituents R²⁵, where

R²² radicals independently of one another are hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkanoyl or (C₃-C₅)-cycloalkyl and

R²³ and R²⁴ independently of one another are (C₁-C₄)-alkyl and

R²⁵ radicals independently of one another are (C₁-C₄)-alkyl,(C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, cyano, nitro,halogen, (C₁-C₄)-alkanoyl or (C₂-C₄)-haloalkanoyl, or two of theradicals

R¹⁶, R¹⁷, R²⁰, R²¹, R²⁵ on the same carbon atom together and in eachcase independently of one another are an oxo group;

and salts thereof, preferably acid addition salts.

Preferred are those compounds of the formula I where

R⁶ is hydrogen, (C₁-C₂₀)-alkyl, (C₂-C₂₀)-alkenyl, (C₂-C₂₀)-alkynyl,(C₃-C₈)-cycloalkyl or (C₄-C₈)-cycloalkenyl and one or more, preferablyup to three, non-adjacent saturated carbon units in the last-mentioned 5radicals can be replaced by a carbonyl group or by hetero atom unitssuch as oxygen, S(O)_(x) where x=0, 1 or 2, NR¹³ or SiR¹⁴R¹⁵, and wherethese last-mentioned 5 radicals, with or without the abovementionedvariations, can optionally be substituted by one or more, preferably upto three, in the case of fluorine up to the maximum number of, identicalor different radicals D¹R¹⁶, or

R⁶ can be aryl or heterocyclyl, it being possible for these two radicalsto be unsubstituted or substituted by up to three, in the case offluorine also up to the maximum number of identical or differentradicals D²R¹⁷, or

R⁴ and R⁶ together form a three- to eight-membered ring system which isspirocyclically linked with the ring system containing the hetero atomsY and Z and in which one or two CH₂ groups, preferably one CH₂ group,can be replaced by hetero atom units such as oxygen, S(O)_(n) where n=0,1 or 2 or NR¹⁸,

where

R¹³ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or (C₁-C₄)-alkanoyl;

R¹⁴ and R¹⁵ independently of one another are (C₁-C₄)-alkyl, preferablymethyl;

R¹⁸ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-alkanoyl, (C₁-C₈)-alkoxy,benzoyl, aryl or heteroaryl, it being possible for the last-mentioned 3radicals to be unsubstituted or to be provided with up to three, in thecase of fluorine also up to the maximum number of, identical ordifferent substituents R¹⁹;

R¹⁹ can be (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkoxy, cyano, nitro or halogen, and the ring system formedby R⁴ and R⁶ can be unsubstituted or provided with up to threesubstituents, but preferably one substituent, D³R²⁰, or the ring systemformed by R⁴ and R⁶ together with a further benzene ring or cyclohexanering together forms a fused ring system, preferably the indane,1,2,3,4-tetrahydronaphthalene, decalin or benzocycloheptane system, andthe benzene ring in these fused systems can be unsubstituted or providedwith up to three, in the case of fluorine also up to the maximum numberof, identical or different substituents D⁴R²¹, where, amongst thecompounds for which the carbon atom between Y and Z only has attached toit the substituent W-R⁶, the substituents X and W-R⁶ are preferably inthe cis-position relative to each other;

D¹, D², D³ and D⁴ are in each case independent of one another and are adirect bond, oxygen, S(O)_(k), SO₂O, OSO₂, CO, OCO, COO, SO₂NR²²,NR²²SO₂, ONR²², NR²²O, SIR²³O, NR²²CO, CONR²² or SiR²³R²⁴, where k is 0,1 or 2; and

R¹⁶, R¹⁷, R²⁰ and R²¹ in each case independently of one another arehydrogen, cyano, nitro, halogen, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl,(C₂-C₈)-alkenyl, (C₂-C₈)-haloalkenyl, (C₂-C₈)alkynyl,(C₂-C₈)-haloalkynyl, (C₁-C₈)-alkoxy (C₁-C₄)-alkyl,(C₁-C₈)-haloalkoxy(C₁-C₄)-alkyl, (C₁-C₈)-alkylthio(C₁-C₄)-alkyl,(C₁-C₈)-haloalkylthio(C₁-C₄)-alkyl, (C₃-C₈)-cycloalkyl,(C₄-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkyl-(C₁-C₄)-alkyl,(C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkyl, aryl, heterocyclyl,aryl-(C₁-C₄)-alkyl or heterocyclyl-(C₁-C₄)-alkyl, it being possible forthe cycloaliphatic, aromatic or heterocyclic ring systems in thelast-mentioned 8 radicals to be unsubstituted or to be provided by up tothree, in the case of fluorine also up to the maximum number of,identical or different substituents R²⁵, where

R²² radicals independently of one another are hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkanoyl or (C₃-C₅)-cycloalkyl and

R²³ and R²⁴ independently of one another are (C₁-C₄)-alkyl and

R²⁵ radicals independently of one another are (C₁-C₄)-alkyl,(C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, cyano, nitro,halogen, (C₁-C₄)-alkanoyl or (C₂-C₄)-haloalkanoyl, or two of theradicals

R¹⁶, R¹⁷, R²⁰, R²¹, R²⁵ on the same carbon atom together and in eachcase independently of one another are an oxo group;

in particular those compounds in which

R⁶ is hydrogen, (C₁-C₈)-alkyl, (C₂-C₈)-alkenyl, (C₂-C₈)-alkynyl,(C₃-C₈)-cycloalkyl or (C₄-C₈)-cycloalkenyl and one or more, preferablyup to three, non-adjacent saturated carbon units in the last-mentioned 5radicals can be replaced by a carbonyl group or by hetero atom unitssuch as oxygen, S(O)_(x) where x=0, 1 or 2, NR¹³ or SiR¹⁴R¹⁵, and wherethese last-mentioned 5 radicals, with or without the abovementionedvariations, can optionally be substituted by one or more, preferably upto three, in the case of fluorine up to the maximum number of, identicalor different radicals D¹R¹⁶, or

R⁶ can be aryl or heterocyclyl, it being possible for these two radicalsto be unsubstituted or substituted by up to three, in the case offluorine also up to the maximum number of identical or differentradicals D²R¹⁷, or

R⁴ and R⁶ together form a five- or six-membered ring system which ispreferably spirocyclically linked to the ring system which contains thehetero atoms Y and Z and in which a CH₂ group can be replaced by heteroatom units such as oxygen, S(O)_(n) where n=0, 1 or 2 or NR¹⁸, where

R¹³ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or (C₁-C₄)-alkanoyl and

R¹⁴ and R¹⁵ independently of one another are (C₁-C₄)-alkyl, preferablymethyl,

R¹⁸ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-alkanoyl, benzoyl, aryl orheteroaryl, it being possible for the last-mentioned 3 radicals to beunsubstituted or to be provided with up to three, in the case offluorine also up to the maximum number of, identical or differentsubstituents R¹⁹ and

R¹⁹ can be (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkoxy, cyano, nitro or halogen and the ring system formedby R⁴ and R⁶ can be unsubstituted or provided with up to threesubstituents, but preferably one substituent, D³R²⁰, or the ring systemformed by R⁴ and R⁶ together forms a fused ring system, preferably theindane, 1,2,3,4-tetrahydronaphthalene, decalin or benzocycloheptanesystem, and the benzene ring in these fused systems can be unsubstitutedor provided with up to three, in the case of fluorine also up to themaximum number of, identical or different substituents D⁴R²¹, where,amongst the compounds for which the carbon atom between Y and Z whereY=CH₂ only has attached to it the substituent W-R⁶, the substituents Xand W-R⁶ are in the cis-position relative to each other;

D¹, D ², D³ and D⁴ are in each case independent of one another and are adirect bond, oxygen, S(O)_(k), SO₂O, OSO₂, CO, OCO, COO, SO₂NR²²,NR²²SO₂, NR²²O, ONR²², NR²², NR²²CO, or CONR²², where k is 0, 1 or 2;and

R²² radicals independently of one another are hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkanoyl or (C₃-C₅)-cycloalkyl, and where

R¹⁶, R¹⁷, R²⁰ and R²¹ in each case independently of one another arehydrogen, cyano, nitro, halogen, preferably fluorine, (C₁-C₈)-alkyl,(C₃-C₈)-cycloalkyl, aryl or heterocyclyl, where the cycloaliphatic,aromatic or heterocyclic ring systems in the last-mentinoed 3 radicalscan be unsubstituted or provided with up to three, in the case offluorine also up to the maximum number of, identical or differentsubstitutents R²⁵, where

R²⁵ radicals independently of one another can be (C₁-C₄)-alkyl,(C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, cyano, nitro,halogen, or two of the radicals

R¹⁶, R¹⁷, R²⁰, R²¹, and R²⁵ on the same carbon atom together and in eachcase independently of one another are an oxo group;

especially preferred are those compounds of the formula I where

R⁶ is (C₁-C₈)-alkyl in which one of more, preferably up to three,non-adjacent saturated carbon units can be replaced by oxygen and which,with or without the abovementioned variations, can optionally besubstituted by one or more, preferably up to three, in the case offluorine up to the maximum number of, identical or different radicalsD¹R²⁰, or

R⁶ can be aryl or heterocyclyl, it being possible for these two radicalsto be unsubstituted or to be substituted by up to three, in the case offluorine also up to the maximum number of, identical or differentradicals D²R²¹.

Furthermore preferred compounds of the formula I are those in which

R¹ is hydrogen, chlorine or fluorine,

R² is (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl,tri-(C₁-C₄)-alkylsilyl -(C₂-C₄)-alkynyl, (C₁-C₄)-haloalkyl, cyclopropyl,halocyclopropyl, methoxymethyl or cyano;

R³ is hydrogen, halogen, methyl, ethyl, ethenyl, ethynyl, methoxy,ethoxy, cyano, trifluoromethyl, fluoromethylthio or methoxycarbonyl; or

R² and R³ together with the carbon atoms to which they are bonded forman optionally substituted unsaturated 5- or 6-membered carbocyclic ringwhich, if it is a 5-membered ring, can contain a sulfur atom instead ofCH₂, or

R² and R³ together with the carbon atoms to which they are bonded form asaturated 5- or 6-membered ring which can contain oxygen or sulfurinstead of a CH₂ group;

A is CH or N;

X is NH or oxygen;

Y is a direct bond or CH₂;

Z is oxygen, NR⁷, S(O)_(m) where m=0,1 or 2;

R⁴ is hydrogen, (C₁-C₄)-alkyl, trifluoromethyl or (C₁-C₄)-alkoxy;

R⁵ is hydrogen;

W is a direct bond, oxygen, —CO—, —COO—, CONR¹², sulfur, —C=N—, —C=N—O—and R¹² in this context can be hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkanoylor (C₃-C₅)-cycloalkyl and

R⁷ is (C₁-C₄)-alkyl;

in particular those compounds in which

R¹ is hydrogen,

R² is methyl, ethyl, propyl, isopropyl, (C₁-C₂)-fluoroalkyl, cyclopropylor methoxymethyl;

R³ is halogen, methyl, ethyl, ethenyl, ethynyl, methoxy, ethoxy,trifluoromethyl, fluoromethylthio, methoxycarbonyl or cyano; or

R² and R³ together with the ring system to which they are bonded formthe quinazoline or quinoline system which can be substituted by fluorinein the carbocyclic moiety; or

R² and R³ together with the carbon atoms to which they are bonded form asaturated 6-membered ring which can contain an oxygen or sulfur atominstead of a CH₂ group;

R⁴ is hydrogen or methyl; and

R⁵ is hydrogen.

Particularly preferred compounds of the formula I are those where

R¹ is hydrogen;

R² is ethyl, propyl, isopropyl, 1-fluoroethyl or methoxymethyl;

R³ is fluorine, chlorine, bromine, cyano, ethenyl, ethynyl or methoxy;or, in the event that A is nitrogen,

R² and R³ together with the ring system to which they are bonded formthe quinazoline system which can be substituted by a fluorine atom;

R⁴ is hydrogen or methyl; and

R⁵ is hydrogen.

Most preferred are those compounds of the formula I in which

R¹ is hydrogen;

R² is ethyl or methoxymethyl;

R³ is fluorine, chlorine, bromine or methoxy; or

A isCH or N;

X is NH;

Z is oxygen and

R⁴ and R⁵ are hydrogen.

In the above formula, “halogen” is to be understood as meaning afluorine, chlorine, bromine or iodine atom;

the term “(C₁-C₄)-alkyl” an unbranched or branched hydrocarbon radicalhaving I to 4 carbon atoms such as, for example, the methyl, ethyl,propyl, isopropyl, 1 -butyl, 2-butyl, 2-methylpropyl or tert-butylradical;

the term “(C₁-C₈)-alkyl” the abovementioned alkyl radicals and also, forexample, the pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, hexyl, heptyl,octyl, or 1,1,3,3-tetramethylbutyl radical;

the term “(C₁-C₂₀)-alkyl” the abovementioned alkyl radicals and also,for example, the nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecylor eicosyl radical;

the term “(C₁-C₄)-haloalkyl” an alkyl group mentioned under the term“(C₁-C₄)-alkyl” in which one or more hydrogen atoms are replaced byhalogen, preferably selected from amongst chlorine and fluorine, suchas, for example, the trifluoromethyl group, the 1-fluoroethyl group, the2-fluoroethyl group, the 2,2,2-trifluoroethyl group, the chloromethyl orfluoromethyl group, the difluoromethyl group or the1,1,2,2-tetrafluoroethyl group;

the term “(C₁-C₂)-fluoroalkyl” for example, the mono-, di- andtrifluoromethyl group, the 1-fluoroethyl, 2-fluoroethyl,1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or apentafluoroethyl group;

the term “cycloalkyl” preferably (C₃-C₈)-cycloalkyl;

the term “cycloalkenyl” preferably (C₄-C₈)-cloalkenyl;

the term “(C₃-C₅)-cycloalkyl” the cyclopropyl, cyclobutyl or cyclopentylgroup;

the term “(C₃-C₈)-cycloalkyl” the radicals mentioned above under“(C₃-C₅)-cycloalkyl” and also the cyclohexyl, cycloheptyl or cyclooctylradical, but also bicyclic systems such as, for example, the norbomylgroup or the bicyclo[2.2.2]octane radical;

the term “(C₃-C₅)-halocycloalkyl” one of the abovementioned(C₃-C₅)-cycloalkyl radicals in which one or more hydrogen atoms arereplaced by halogen, preferably selected from amongst chlorine andfluorine, such as, for example, the 2,2-difluoro-or2,2-dichlorocyclopropane group or the fluorocyclopentane radical;

the term “(C₂-C₄)-alkenyl” for example the vinyl, allyl,2-methyl-2-propenyl or 2-butenyl group;

the term “(C₂-C₈)-alkenyl” the abovementioned radicals and, for example,the 2-pentenyl or the 2-octenyl group;

the term “(C₂-C₂₀)-alkenyl” the abovementioned radicals and also, forexample, the 2-decenyl or the 2-eicosenyl group;

the term “(C₂-C₄)-haloalkenyl” a (C₂-C₄)-alkenyl group in which one ormore hydrogen atoms are replaced by halogen, preferably selected fromamongst chlorine and fluorine,

the term “(C₂-C₈)-haloalkenyl” a (C₂-C₈)-alkenyl group in which one ormore hydrogen atoms are replaced by halogen, preferably selected fromamongst chlorine and fluorine;

the term “(C₄-C₅)-cycloalkenyl” the cyclobutenyl or cyclopentenyl group;

the term “(C₄-C₈)-cycloalkenyl” the abovementioned radicals and also,for example, the 2-cyclohexenyl or the 2-cyclopentenyl group;

the term “(C₂-C₄)-alkynyl”, for example, the ethynyl, the propargyl, orthe 1-butynyl, 2-butynyl or 3-butynyl group;

the term “(C₂-C₈)-alkynyl” the abovementioned radicals and also, forexample, the 2-pentynyl or the 2-octynyl group,

the term “(C₂-C₂₀)-alkynyl” the abovementioned radicals and also, forexample, the 2-decynyl group;

the term “(C₂-C₄)-haloalkynyl” a (C₂-C₄)-alkynyl group in which one ormore hydrogen atoms are replaced by halogen, preferably selected fromamongst chlorine and fluorine, or else the iodoethynyl group;

the term “(C₂-C₈)-haloalkynyl” a (C₂-C₈)-alkynyl group in which one ormore hydrogen atoms are replaced by halogen, preferably selected fromamongst chlorine and fluorine;

the term “tri-(C₁-C₄)-alkylsilyl-(C₂-C₄)-alkynyl” preferably thetrimethylsilylethynyl group;

the term “(C₁-C₄)-hydroxyalkyl” for example the hydroxymethyl,1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-1methylethyl or the1-hydroxypropyl group;

the term “(C₁-C₄)-alkanoyl” for example the formyl, acetyl, propionyl,2-methylpropionyl or butyryl group;

the term “(C₂-C₄)-haloalkanoyl” a (C₂-C₄)-alkanoyl group in which one ormore hydrogen atoms are replaced by halogen, preferably selected fromamongst chlorine and fluorine;

the term “cyano-(C₁-C₄)-alkyl” a cyanoalkyl group whose hydrocarbonradical has the meanings given for the term “(C₁-C₄)-alkyl”;

the term “(C₁-C₄)-alkoxycarbonyl” for example the methoxycarbonyl,ethoxycarbony, propoxycarbonyl, butoxycarbonyl or tert-butoxycarbonylgroup;

the term “(C₁-C₄)-haloalkoxycarbonyl” a (C₁-C₄)-alkoxycarbonyl group inwhich one or more hydrogen atoms are replaced by halogen, preferablyselected from amongst chlorine and fluorine;

the term “(C₁-C₄)-alkylthio” an alkylthio group whose hydrocarbonradical is as defined for the term “(C₁-C₄)-alkyl”;

the term “(C₁-C₄)-haloalkylthio” a (C₁-C₄)-alkylthio group in which oneor more hydrogen atoms are replaced by halogen, preferably selected fromamongst chlorine and fluorine;

the term “fluoromethylthio” the mono-, di- and trifluoromethylthiogroup;

the term “(C₁-C₄)-alkylsulfinyl” for example the methyl-, ethyl-,propyl-, isopropyl-, butyl-, isobutyl-, sec-butyl- or tert-butylsulfinylgroup;

the term “(C₁-C₄)-alkylsufonyl” for example the methyl-, ethyl-,propyl-, isopropyl-, butyl-, isobutyl-, sec-butyl- or tert-butylsulfonylgroup;

the terms “(C₁-C₄)-haloalkylsulfinyl” and “(C₁-C₄)-haloalkylsulfonyl”(C₁-C₄)-alkylsulfinyl- and (C₁-C₄)-alkylsulfonyl radicals as definedabove in which one or more hydrogen atoms are replaced by halogen,preferably selected from amongst chlorine and fluorine;

the term “(C₁-C₄)-alkoxy” an alkoxy group whose hydrocarbon radical isas defined for the term “(C₁-C₄)-alkyl”;

the term “(C₃-C₅)-cycloalkoxy” for example the cyclopropoxy, cyclobutoxyor the cyclopentoxy group;

the term “(C₁-C₄)-haloalkoxy” a haloalkoxy group whose halohydrocarbonradical is as defined for the term “(C₁-C₄)-haloalkyl”;

the term “(C₁-C₄)-alkoxy-(C₁-C₄)-alkyl” for example a 1-methoxyethylgroup, a 2-methoxyethyl group, a 2-ethoxyethyl group, a methoxymethyl orethoxymethyl group, a 3-methoxypropyl group or a 4-utoxybutyl group;

the terms “(C₁-C₄)-haloalkoxy-(C₁-C₄)-alkyl”,“(C₁-C₄)-alkoxy-(C₁-C₄)-haloalkyl” and“(C₁-C₄)-haloalkoxy-(C₁-C₄)-haloalkyl” (C₁-C₄)-alkoxy-(C₁-C₄)-alkylradicals as defined above in which one or more hydrogen atoms arereplaced by halogen, preferably selected from amongst chlorine andfluorine;

the term “(C₁-C₄)-alkylthio-(C₁-C₄)-alkyl” for example methylthiomethyl,ethylthiomethyl, propylthiomethyl, 2-methylthioethyl, 2-ethylthioethylor 3-methylthiopropyl;

the term “aryl” a carbocyclic aromatic radical having preferably 6 to14, in particular 6 to 12, carbon atoms such as, for example, phenyl,naphthyl or biphenylyl, preferably phenyl;

the term “heterocyclyl” a heteroaromatic or heteroaliphatic ring system,“heteroaromatic ring system” to be understood as meaning an aryl radicalin which at least one CH group is replaced by N and/or at least twoadjacent CH groups are replaced by S, NH or O, for example a radical ofthiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole,isoxazole, pyrazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole,1,3,4-triazole, 1,2,4-oxadiazole, 1,2,4-thiadiazole, 1,2,4-triazole,1,2,3-triazole, 1,2,3,4-tetrazole, benzo[b]thiophene, benzo[b]furan,indole, benzo[c]thiophene, benzo[c]furan, isoindole, benzoxazole,benzothiazole, benzimidazole, benzisoxazole, benzisothiazole,benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran,dibenzothiophene, carbazole, pyridine, pyrazine, pyrimidine, pyridazine,1,3,5-triazine, 1,2,4-triazine, 1,2,4,5-triazine, quinoline,isoquinoline, quinoxaline, quinazoline, cinnoline, 1,8-naphthyridine,1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine,pyridopyrimidine, purine, pteridine or 4H-quinolizine;

and the term “heteroaliphatic ring system” a (C₃-C₈)-cycloalkyl radicalin which at least one carbon unit is replaced by O, S or a group NR¹²and R¹² is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or aryl;

What has been explained above applies analogously to homologs orradicals derived therefrom.

The present invention relates to the compounds of the formula I in theform of the free basis or of an acid addition salt. Acids which can beused for salt formation are inorganic acids such as hydrochloric acid,hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, ororganic acids such as formic acid, acetic acid, propionic acid, malonicacid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid,methanesulfonic acid, benzenesuffonic acid or toluenesulfonic acid.

Beside the abovementioned cis/trans isomerism on the hetero-cycloalkylgroup, some of the compounds of the formula I have one or more symmetriccarbon atoms or stereoisomers on double bonds. Enantiomers ordiastereomers are therefore possible. The scope of the invention extendsto the pure isomers and also to mixtures of these. The diastereomermixtures can be separated into the components by customary methods, forexample by selective crystallization from suitable solvents or bychromatography. Racemates can be resolved by customary methods to givethe enantiomers, for example by salt formation with an optically activeacid, separation of the diastereomeric salts and liberation of the pureenantiomers by means of a base.

The invention furthermore relates to a process for the preparation ofcompounds of the formula I which comprises reacting a compound of theformula II

where A, R¹, R² and R³ are as defined for formula I and L is a leavinggroup, for example halogen, alkylthio, alkanesulfonyloxy orarylsulfonyloxy, alkylsulfonyl or arylsulfonyl, with a nucleophile ofthe formula III

where W, X, Y, Z, R⁴, R⁵ and R⁶ are as defined above for formula I and,if appropriate, further derivatizing the nitrogen heterocycle or theside chain R⁶ in the compounds of the formula I obtained in the above orany other manner.

The above-described substitution reaction is known in principle. Theleaving group L can be varied within wide limits and can be, forexample, a halogen atom such as fluorine, chlorine, bromine or iodine,or alkylthio such as methyl- or ethylthio, or alkanesulfonyloxy such asmethane-, trifluoromethane- or ethanesulfonyloxy or arylsulfonyloxy,such as benzenesulfonyloxy or toluenesulfonyloxy, or alkyl sulfonyloxysuch as methyl- or ethylsulfonyl, or arylsulfonyl such as phenyl- ortoluenesulfonyl.

The abovementioned reaction was carried out in a termperature range offrom 20 to 1 50° C., expediently in the presence of a base and, ifappropriate, in an inert organic solvent such as, for example,N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide,N-methylpyrrolidin-2-one, dioxane, tetrahydrofuran,4-methyl-2-pentanone, methanol, ethanol, butanol, ethylene glycol,ethylene glycol dimethyl ether, toluene, chlorobenzene or xylene.Mixtures of the abovementioned solvents can also be used.

In the event that X is oxygen, examples of suitable bases are alkalimetal carbonates, alkali metal hydrogen carbonates, alkali metal amides,alkali metal hydrides, alkaline earth metal carbonates, alkaline earthmetal hydrogen carbonates, alkaline earth metal amides or alkaline earthmetal hydrides such as sodium carbonate, sodium hydrogen carbonate,potassium carbonate, sodium amide or sodium hydride, and in the eventthat X is NH, examples of suitable bases are alkali metal carbonates,alkali metal hydrogen carbonates, alkali metal hydroxides, alkali metalamides, alkali metal hydrides, alkaline earth metal carbonates, alkalineearth metal hydrogen carbonates, alkaline earth metal hydroxides,alkaline earth metal amides or alkaline earth metal hydrides such assodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodiumhydroxide, sodium amide or sodium hydride or organic bases such astriethylamine or pyridine. A second equivalent of an amine of theformula III can also be employed as auxiliary base.

Most of the compounds of the formula II which are required as startingmaterials are known from the literature or can be prepared analogouslyto known methods (cf. EP 370 391, EP 470 600, DOS 43 31 179, DOS 44 04702.)

To prepare the nucleophiles of the formula III, suitably substitutedcations of the formula IV are used as starting materials and areconverted into the corresponding amines by reductive amination (H₂, NH₃,metal catalyst or ammonium acetatelsodium cyanoborohydride orLeuckart-Wallach reduction) or into the corresponding alcohols byreduction with a complex metal hydride.

Furthermore, the nucleophiles of the formula III where X=NH can beprepared by reducing an oxime or imine or by subjecting an alkyl halideor alkyl tosylate by a Gabriel reaction or a Mitsunobu reaction withphthalimide and subsequent hydrazinolysis. Equally, these nucleophilescan be synthesized by reacting an alkyl halide or alkyl tosylate with ametal azide and reducing the azide with a suitable reducing agent, forexample a complex metal hydride, hydrogen in the presence of ahydrogenation catalyst or phosphine or phosphite. The alkyl halides oralkyl tosylates are accessible from the alcohols of formula V.

The ketones of the formula IV or the alcohols of the formula V are knownfrom the literature or can be synthesized analogously to known processes(cf. M. A. Gianturco, P. Friedel, A. S. Giammarino, Tetrahedron 1964,20, 1763. U.S. Pat. No. 4,388,104. Y. Senda, T. Terasawa, I. lshiyama,S. Kamiyama, S. Imaizuma, Bull. Chem. Soc. Jpn. 1989, 62, 2948.

D. N. Reinhardt, W. P. Trompenaars, I. Geevers, Synthesis 1976, 368.

Curtis W. Smith, D. G. Norton, S. A. Ballard, J. Am. Chem. Soc. 1951,73, 5267).

The active substances are well tolerated by plants and have a favorabletoxicity to warm-blooded species and are suitable for controlling animalpests, in particular insects, arachnids, helminths and molluscs andtheir eggs, very especially preferably for controlling insects andarachnids found in agriculture, in livestock breeding, in forests, inthe protection of stored products and materials and in the hygienesector. They are effective against normally sensitive and resistantspecies and all or some developmental stages. The abovementioned pestsinclude: From the order of the Acarina, for example Acarus siro, Argasspp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis,Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyommaspp., Hyalomma spp., lxodes spp., Psoroptes spp., Chorioptes spp.,Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp.,Tetranychus spp., Eotetranychus spp., Oligonychus spp., Eutetranychusspp.

From the order of the Isopoda, for example, Oniscus asselus, Armadiumvulgar, Porcelio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus,Scutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea madeirae, Blatella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis, Schistocerca gregaria.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Phylloera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp.,Linognathus spp.

From the order of the Mallophaga, for example, Trichodectes pp.,Damalinea spp.

From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus, Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelus bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp., Psylia spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonelIa, Cacoecia podana,Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homonamagnanima, Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylloides chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonumus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrynchus assimilis, Hypera postica, Dermestes spp., Trogoderma,Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinusspp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebriomolitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hypobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscineliafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopsis,Ceratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus,Latrodectus mactans.

From the class of the helminths, for example, Haemonchus,Trichostrongulus, Ostertagia, Cooperia, Chabertia, Strongyloides,Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris and Heterakis andalso Fasciola.

From the class of the gastropods, for example, Deroceras spp., Arionspp., Lymnaea spp., Galba spp., Succinea spp., Biomphalaria spp.,Bulinus spp., Oncomelania spp.

From the class of the bivalves, for example, Dreissena spp.

The plant-parasitic nematodes which can be controlled according to theinvention include, for example, the root-parasitic soil nematodes suchas, for example, those from the genera Meloidogyne (root-knot nematodes,such as Meloidogyne incognita, Meloidogyne hapla and Meloidogynejavanica), Heterodera and Globodera (cyst-forming nematodes, such asGlobodera rostochiensis, Globodera pallida, Heterodera trifolii) andfrom the genera Radopholus, such as Radopholus similis, Pratylenchus,such as Pratylenchus neglectus, Pratylenchus penetrans and Pratylenchuscurvitatus;

Tylenchulus, such as Tylenchulus semipenetrans, Tylenchorhynchus, suchas Tylenchorhynchus dubius and Tylenchorhynchus claytoni, Rotylenchus,such as Rotylenchus robustus, Heliocotylenchus, such as Haliocotylenchusmulticinctus, Belonoaimus, such as Belonoaimus longicaudatus,Longidorus, such as Longidorus elongatus, Trichodorus, such asTrichodorus primitivus and Xiphinema, such as Xiphinema index.

Furthermore, the compounds according to the invention can be used forcontrolling the nematode genera Ditylenchus (stem parasites, such asDitylenchus dipsaci and Ditylenchus destructor), Aphelenchoides (foliarnematodes, such as Aphelenchoides ritzemabosi) and Anguina (seednematodes, such as Anguina tritici).

The invention also relates to compositions, in particular toinsecticidal, acaricidal and ovicidal compositions, which comprise thecompounds of the formula I in addition to suitable formulationauxiliaries.

The compositions according to the invention comprise the activeingredients of the formula I in a concentration range of from 0.00000001to 95% by weight, preferably from 1 to 95% by weight.

They can be formulated in various ways, depending on the prevailingbiological and/or chemico-physical parameters. The followingformulations are therefore possible:

Wettable powders (WP), emulsifiable concentrates (EC), aqueous solutions(SL), emulsions, sprayable solutions, oil- or water-based dispersions(SC), suspoemulsions (SE), dusts (DP), seed-treatment products, granulesin the form of microgranules, spray granules, coated granules andadsorption granules, water-dispersible granules (WG), ULV formulations,microcapsules, waxes or baits.

These individual types of formulation are known in principle and aredescribed, for example, in:

Winnacker-KuchIer, “Chemische Technologie” [Chemical Engineering],Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986; van Falkenberg,“Pesticides Formulations”, Marcel Dekker N.Y., 2nd Ed. 1972-73; K.Martens, “Spray Drying Handbook”, 3rd Ed. 1979, G. Goodwin Ltd. London.

The formulation auxiliaries required, such as inert materials,surfactants, solvents and other additives are also known and aredescribed, for example, in:

Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd Ed.,Darland Books, Caldwell N.J.; H. v. Olphen, “Introduction to ClayColloid Chemistry”, 2nd Ed., J. Wiley & Sons, N.Y.; Marsden, “SolventsGuide”, 2nd Ed., lnterscience, N.Y. 1950; McCutcheon's, “Detergents andEmulsifiers Annual”, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood,“Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y.1964; Schönfeldt, “Grenzflächenaktive Äthylenoxidaddukte”[Surface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart1967; Winnacker-Küchler, “Chemische Technologie” [Chemical Engineering],Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986.

Based on these formulations, it is also possible to prepare combinationswith other pesticidally active substances, fertilizers andlor growthregulators, for example in the form of a ready mix or a tank mix.Wettable powders are preparations which are uniformly dispersible inwater and which, beside the active substance, also comprise wettingagents, for example polyoxyethylated alkylphenols, polyoxyethylatedfatty alcohols, alkyl- or alkylphenylsulfonates and dispersants, e.g.sodium lignosulfonate and sodium2,2′-dinaphthylmethane-6,6′-disulfonate, in addition to a diluent orinert substance.

Emulsifiable concentrates are prepared by dissolving the activesubstance in an organic solvent, for example butanol, cyclohexanone,dimethylformamide, xylene, or else higher-boiling aromatics orhydrocarbons with addition of one or more emulsifiers. Emulsifiers whichcan be used are ionic emulsifiers such as, for example, calciumalkylarylsulfonates, such as calcium dodecylbenzenesulfonate, ornon-ionic emulsifiers such as, for example, fatty acid polyglycolesters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers,propylene oxidelethylene oxide condensates, alkyl polyethers, sorbitanfatty acid esters, polyoxyethylene sorbitan fatty acid esters orpolyoxyethylene sorbitol esters.

Dusts are obtained by grinding the active substance with finely dividedsolid substances, for example talc, natural clays such as kaolin,bentonite, pyrophyllite or diatomaceous earth. Granules can be preparedeither by spraying the active substance onto adsorptive granulated inertmaterial or by applying active substance concentrates to the surface ofcarriers such as sand, kaolinites or granulated inert material with theaid of binders, for example polyvinyl alcohol, sodium polyacrylate orelse mineral oils. Suitable active substances can also be granulated inthe manner customary for the preparation of fertilizer granules, ifdesired in a mixture with fertilizers.

In wettable powders, the active substance concentration is, for example,approximately 10 to 90% by weight, the remainder to 100% being composedof customary formulation components. In the case of emulsifiableconcentrates, the active substance concentration can amount toapproximately 5 to 80% by weight. Formulations in the form of dustsusually comprise 5 to 20% by weight of active substance, sprayablesolutions approximately 2 to 20% by weight. In the case of granules, theactive substance content depends partly on whether the active compoundis in liquid or solid form and on which granulation auxiliaries, fillersand the like are being used.

Additionally, the abovementioned formulations of active substancescomprise, if appropriate, the tackifiers, wetting agents, dispersants,emulsifiers, penetrants, solvents, fillers or carriers which arecustomary in each case.

For use, the concentrates which are in commercially available form are,if appropriate, diluted in the customary manner, for example by means ofwater in the case of wettable powders, emulsifiable concentrates,dispersions and in some cases also microgranules. Preparations in theform of dusts and granules and sprayable solutions are usually notdiluted further with other inert substances prior to use.

The rate of application required varies with the external conditionssuch as, inter alia, temperature and humidity. It can vary within widelimits, for example between 0.0005 and 10.0 kg/ha or more activesubstance, but it is preferably between 0.001 and 5 kg/ha.

The active substances according to the invention can be present in theircommercially available formulations and in the use forms prepared fromthese formulations in the form of mixtures with other active substances,such as insecticides, attractants, sterilants, acaricides, nematicides,fungicides, ovicides, growth regulators or herbicides.

The pesticides include, for example, phosphoric esters, carbamates,carboxylic esters, formamidines, tin compounds, substances produced bymicroorganisms and the like.

Preferred components for mixtures are:

1. from the group of the phosphorus compounds acephate, azamethiphos,azinphosethyl, azinphosmethyl, bromophos, bromophosethyl,chlorfenvinphos, chlormephos, chiorpyrifos, chlorpyrifos-methyl,demeton, demeton-S-methyl, demeton-S-methylsulfone, dialifos, diazinon,dichlorvos, dicrotophos, O,O-1,2,2,2-tetrachloroethylphosphorothioate(SD 208 304), dimethoate, disulfoton, EPN, ethion, ethoprophos,etrimfos, famphur, fenamiphos, fenitriothion, fensulfothion, fenthion,fonofos, formothion, heptenophos, isozophos, isothioate, isoxathion,malathion, methacrifos, methamidophos, methidathion, salithion,mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl,parathion, parathion-methyl, phenthoate, phorate, phosalone, phosfolan,phosmet, phosphamidon, phoxim, pirimiphos, pirimiphos-ethyl,pirimiphos-methyl, profenofos, propaphos, proetamphos, prothiofos,pyraclofos, pyridapenthion, quinalphos, suiprofos, temephos, terbufos,tetrachlorvinphos, thiometon, triazophos, trichlorphon, vamidothion;

2. from the group of the carbamates aldicarb, 2-secbutylphenylmethylcarbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb,benfuracarb, ethiofencarb, furathiocarb, isoprocarb, methomyl,5-methyl-m-cumenyl butyryl(methyl)carbamate, oxamyl, pirimicarb,propoxur, thiodicarb, thiofanox, ethyl4,6,9-triaza-4-benzyl,-6,10-dimethyl-8-oxa-7-oxo5,11-dithia-9-dodecenoate(OK 135), 1-methylthio(ethylideneamino)-N-methyl-N-(morpholinothio)carbamate (UC 51717);

3. from the group of the carboxylic esters allethrin, alphametrin,5-benzyl-3-furylmethyl (E)-(1R)-cis,2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate,bioallethrin, bioallethrin ((S) cyclopentyl isomer), bioresmethrin,biphenate, (RS)-1-cyano-1-(6-phenoxy-2-pyridyl)methyl(1RS)-trans-3-(4-tert-butylphenyl)-2,2-dimethylcyclopropanecarboxylate(NCI 85193), cycloprothrin, cyhalothrin, cythithrin, cypermethrin,cyphenothrin, deltamethrin, empenthrin, esfenvalerate, fenfluthrin,fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (Disomer), permethrin, pheothrin ((R)-isomer), d-pralethrin, pyrethrins(natural products), resmethrin, tefluthrin, tetramethrin, tralomethrin;

4. from the group of the amidines amitraz, chlordimeform;

5. from the group of the tin compounds cyhexatin, fenbutatinoxide;

6. others abamectin, Bacillus thuringiensis, bensultap, binapacryl,bromopropylate, buprofezin, camphechlor, cartap, chlorobenzilate,chlorfluazuron, 2-(4-chlorophenyl)-4,5-diphenylthiophene (UBI-T930),chlorfentezine, 2-naphthylmethyl cyclopropanecarboxylate (Ro12-0470),cyromazin, ethylN-(3,5-dichloro-4-(1,1,2,3,3,3-hexafluoro-1-propyloxy)phenyl)carbamoyl)-2-chlorobenzocarboximidate,DDT, Dicofol,N-(N-(3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy)phenylamino)carbonyl)-2,6-difluorobenzamide(XRD 473), diflubenzuron,N-(2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene)-2,4-xylidine, dinobuton,dinocap, endosulfan, ethofenprox,(4-ethoxyphenyl)(dimethyl)(3-(3-phenoxyphenyl)propyl)silane,(4-ethoxyphenyl)(3-(4-fluoro-3-phenoxyphenyl)propyl)dimethylsilane,fenoxycarb, 2-fluoro-5-(4-(4-ethoxyphenyl)-4-methyl-1-pentyl) diphenylether (MTI 800), granulosis and nuclear polyhedrosis viruses,fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, gamma-HCH,hexythiazox, hydramethyinon (AC 217300), ivermectin,2-nitromethyl-4,5-dihydro-6H-thiazine (DS 52618),2-nitromethyl-3,4-dihydrothiazole (SD 35651),2-nitromethylene-1,2-thiazinan-3-ylcarbamaldehyde (WL 108477),propargite, teflubenzuron, tetradifon, tetrasul, thiocyclam, trifumuron,imidacloprid.

The active substance content of the use forms prepared from thecommercially available formulations can range from 0.00000001 to 95% byweight of active substance, it is preferably between 0.00001 and 1% byweight.

They are applied in a customary manner adapted to the use forms.

The active substances according to the invention are also suitable forcontrolling endo- and ectoparasites in the field of veterinary medicineand in the field of animal keeping.

The active substances according to the invention are applied by oraladministration, for example in the form of tablets, capsules, drinks,granules, by dermal administration, for example by dipping, spraying,pouring-on and spotting-on and dusting, and also by parenteraladministration, for example by means of an injection, e.g. s.c.

Accordingly, the novel compound of the formula I according to theinvention can also be employed especially advantageously in livestockkeeping (for example cattle, sheep, pigs and poultry such as chickens,geese, and the like). In a preferred embodiment of the invention, thenovel compounds are administered orally to the animals, if appropriatein the form of suitable formulations (cf. above) and if appropriatetogether with the drinking water or feed. Since elimination with thefeces is efficient, this enables the prevention of the development ofinsects in the animal's feces in a simple manner. The dosages andformulations which are suitable in each case depend, in particular, onthe species and the developmental stage of the productive livestock andalso on the infection pressure and can be readily determined andestablished by the customary methods. In the case of cattle, the novelcompounds can be employed for example at dosages of from 0.01 to 1 mg/kgbodyweight.

The compounds of the formula I according to the invention are alsodistinguished by an outstanding fungicidal activity. Fungal pathogenswhich have already penetrated the plant tissue can be controlledsuccessfully in a curative fashion. This is especially important andadvantageous in the case of those fungal diseases which can no longer becontrolled efficiently with the otherwise customary fungicides onceinfection has set in. The spectrum of action of the claimed compoundsincludes a variety of economically important phytopathogenic fungi suchas, for example, Plasmopara viticola, Phytophthora infestans, Erysiphegraminis, Pyricularia oryzae, Pyrenophora teres, Leptosphaerea nodorumund Pellicularia sasakii and Puccinia recondite.

The compounds according to the invention are in addition also suitablefor use in industrial fields, for example as wood preservatives, aspreservatives in paints, in cooling lubricants for metalworking, or aspreservatives in drilling and cutting oils.

The active substances according to the invention can be used in theircommercially available formulations either alone or in combination withother fungicides known from the literature.

Fungicides known from the literature which can be combined in accordancewith the invention with the compounds of the formula I are, for example,the following products:

aldimorph, andoprim, anilazine, BAS 480F, BAS 450F, BAS 490F, benalaxyl,benodanil, benomyl, binapacryl, bitertanol, bromuconazole, buthiobate,captafol, captan, carbendazim, carboxin, CGA 173506, cyprodinil,cyprofuram, dichiofluanid, dichlomezin, diclobutrazol, diethofencarb,difenconazole (CGA 169374), difluconazole, dimethirimol, dimethomorph,diniconazole, dinocap, dithianon, dodemorph, dodine, edifenfos,ethirimol, etridiazole, epoxiconazole, fenbuconazole, fenarimol,fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,fentin hydroxide, ferimzone (TF164), fluazinam, fluobenzimine,fludioxinil, fluquinconazole, fluorimide, flusilazole, flutolanil,flutriafol, folpet, fosetyl-aluminum, fuberidazole, fulsulfamide (MT-F651), furalaxyl, furconazole, furmecyclox, guazatine, hexaconazole, ICIA5504, imazalil, imibenconazole, iprobenfos, iprodione, isoprothiolane,KNF 317, copper compounds such as copper oxychloride, oxine-copper,copper oxide, mancozeb, maneb, mepanipyrim (KIF 3535), metconazol,mepronil, metalaxyl, methasulfocarb, methfuroxam, MON 24000,myclobutanil, nabam, nitrothalidopropyl, nuarimol, ofurace, oxadixyl,oxycarboxin, penconazole, pencycuron, PP 969, probenazole, propineb,prochloraz, procymidon, propamocarb, propiconazole, prothiocarb,pyracarbolid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,rabenzazole, RH7592, sulfur, tebuconazole, TF 167, thiabendazole,thicyofen, thiofanate-methyl, thiram, toiclofos-methyl, tolylfluanid,triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph,triflumizole, triforine, trifionazol, validamycin, vinchlozolin, XRD563, zineb, sodium dodecylsulfonate, sodium dodecyl sulfate, sodiumC13/C15-alcohol ether sulfonate, sodium cetostearyl phosphate ester,sodium dioctylsulfosuccinate, sodium isopropylnaphthalene-sulfonate,sodium methylenebisnaphthalenesulfonate, cetyltrimethylammoniumchloride, salts of long-chain primary, secondary or tertiary amines,alkylpropyleneamines, laurylpyrimidinium bromide, ethoxylated quatemizedfatty amides, alkyidimethylbenzylammonium chloride and1-hydroxyethyl-2-alkyl-imidazoline.

The abovementioned components in combinations are known activesubstances, many of which are described in Ch.R Worthing, S. B. Walker,The Pesticide Manual, 7th edition (1983), British Crop ProtectionCouncil. The active substance content of the use forms prepared from thecommercially available formulations can vary within wide ranges, theactive substance concentration of the use forms can amount to from0.0001 to 95% by weight of active substance, it is preferably between0.0001 and 1% by weight. They are applied in a customary manner adaptedto suit the use forms.

The examples which follow are intended to illustrate the inventionwithout imposing any limitation thereto.

A. FORMULATION EXAMPLES

a) A dust was obtained by mixing 10 parts by weight of active substanceand 90 parts by weight of talc as inert substance and comminuting themixture in a hammer mill.

b) A wettable powder which was readily dispersible in water was obtainedby mixing 25 parts by weight of active substance, 65 parts by weight ofkaolin-containing quartz as inert substance, 10 parts by weight ofpotassium lignosulfonate and 1 part by weight of sodiumoleoylmethyltaurinate as wetting agent and dispersant and grinding themixture in a pinned-disk mill.

c) A dispersion concentrate which is readily dispersible in water wasprepared by mixing 40 parts by weight of active substance with 7 partsby weight of sulfosuccinic monoester, 2 parts by weight of a sodiumlignosulfosuccinate and 51 parts by weight of water and grinding themixture in a ball mill to a fineness of below 5 microns.

d) An emulsifiable concentrate was prepared from 15 parts by weight ofactive substance, 75 parts by weight of cyclohexane as solvent and 10parts by weight of oxyethylated nonylphenol (10 EO) as emulsifier.

e) Granules were prepared from 2 to 15 parts by weight of activesubstance and an inert carrier material for granules such asattapulgite, pumice granules andlor quartz sand. Expediently, asuspension of the wettable powder from Example b) with a solids contentof 30% was used; this was sprayed onto the surface of attapulgitegranules and the latter were dried and mixed intimately. The wettablepowder amounted to approximately 5% by weight and the inert carriermaterial to approximately 95% of the finished granules.

B. Preparation Examples

1.) 5-Chloro-6-ethyl-4-(2-phenyltetrahydrofuran-4-ylamino)pyrimidine

1.50 g (8.5 mmol) of 4,5-dichloro-6-ethylpyrimidine, 1.39 g (8.5 mmol)of 4-amino-2-phenyltetrahydrofuran and 2 ml (14 mmol) of triethylaminewere heated for 12 hours at 85° C. After cooling, the mixture wasdiluted with water and extracted with ether, and the organic phase waswashed with saturated NaCl solution. After the mixture had been driedand concentrated, the residue was purified by column chromatographyusing petroleum etherlethyl acetate (9:1, 8:2). This gave 1.63 g (63% oftheory) of a colorless oil (diastereomers 1:1).

2.) Preparation of 4-amino-2-phenyltetrahdyrofuran

11.5 g (61 mmol) of 4-azido-2-phenyltetrahydrofuran in 50 ml of THF wereadded dropwise in the course of 15 minutes at 0° C. to a suspension of3.46 g (91.1 mmol) of lithium aluminum hydride in 200 ml of THF. Themixture was stirred for 30 minutes at room temperature and refluxed for1 hour. After the mixture had been cooled to 0° C., excess alanate wasdestroyed using isopropanol, and the mixture was diluted with 500 ml ofether and washed with saturated tartrate solution and saturated NaClsolution. After the organic phase had been dried and concentrated, theresulting colorless oil was further employed directly. Yield: 9.4 g (95%of theory).

3.) Preparation of 4-azido-2-phenyltetrahydrofuran

14.7 g (61 mmol) of 4-methanesulfonyloxy-2-phenyltetrahydrofuran and5.13 g (79 mmol) of sodium azide were heated for 3 hours in 120 ml ofDMF at 90° C. After the mixture had cooled, it was diluted with ether,washed with water and saturated NaCl solution, dried and concentrated invacuo. This gave 9.4 g (quant.) of a colorless oil, which was furtherreacted directly.

4.) Preparation of 4-methanesulfonyloxy-2-phenyltetrahydrofuran

9.2 g (79 mmol) of methanesulfonyl chloride were added dropwise at 0° C.to a solution of 10 g (61 mmol) of 2-phenyltetrahydrofuran-4-ol and 9.2g (91 mmol) of triethylamine in 150 ml of dichlormethane. The mixturewas stirred for 1 hour at 0° C. and then washed with water, 2Nhydrochloric acid, saturated NaHCO₃ solution and saturated NaClsolution. Drying and concentrating gave 14.7 g (quant.) of mesylate,which was employed further without purification.

5.) Preparation of 2-phenyltetrahydrofuran-4-ol

10 ml of a 60% HClO₄ solution was added at 0° C. to a solution of 15 g(91 mmol) of 1-phenyl-3-buten-1-ol epoxide in 400 ml of water/300 ml ofacetone. The mixture was stirred for 24 hours at room temperature, 40 mlof concentrated H₂SO₄ were added at 0° C., and the mixture was refluxedfor 8 hours. After cooling, the mixture was extracted withdichloromethane (3×), washed with saturated NaHCO₃, dried andconcentrated. Purification by column chromatography usingdichlormethanelacetone (9:1, 8:2) gave 10 g (67% of theory) of acolorless oil.

6.) Preparation of 1-phenyl-3-buten-1-ol epoxide

100 ml of hydrogen peroxide (30%) were added dropwise at 0° C. to asolution of 15 g (101 mmol) of 1-phenyl-3-buten-1-ol and 5.5 g (30 mmol)of tetramethylammonium hydroxide in 400 ml of acetonitrile. The mixturewas stirred for 4 hours at 0° C. and for 8 hours at room temperature.The mixture was subsequently diluted with ether, the phases wereseparated, and the organic phase was washed with saturated NaClsolution. Drying and concentrating gave 15 g (90% of theory) of acolorless oil, which was further employed directly.

7.) Preparation of 1-phenyl-3-buten-1-ol

39 g (0.6 mol) of zinc powder were added at 0° C., a little at a time,to a solution of 53 g (0.5 mol) of benzaldehyde and 73 g (0.6 mol) ofallyl bromide in 500 ml of saturated NH₄Cl solution/100 ml of THF. Themixture was stirred for 4 hours at room temperature and diluted withether, and the solid constituents were filtered off with suction. Afterwashing with ether, the phases were separated, and the organic phase waswashed with water (2×) and saturated NaCl solution. Drying andconcentrating gave 65.2 g (88% of theory) of a colorless oil which wasfurther employed directly.

1.) 5-Chloro-6-ethyl-4-(2-methyltetrahydrofuran-4-ylamino)pyrimidine

1.5 g of 4,5-dichloro-6-ethylpyrimidine (8.5 mmol), 0.86 g (8.5 mmol) of4-amino-2-methyltetrahydrofuran (prepared from2-methyltetrahydrofuran4-ol analogously to the route given for ExampleA) and 2 ml (14 mmol) of triethylamine were heated for 6 hours at 85° C.After cooling, the mixture was diluted with water and extracted withether, and the organic phase was washed with saturated NaCl solution.After drying and concentrating, the residue was purified by columnchromatography using petroleum ether/ethyl acetate (8:2, 7:3). This gave1.73 g (84% of theory) of a colorless oil (diastereomers 2:1).

2.) Preparation of the starting material 2-methyltetrahydrofuran-4-ol

4.6 g (0.121 mol) of sodium borohydride were added in portions at 0° C.to a solution of 12.1 g (0.121 mol) of 2-methyltetrahydrofuran-4-one (M.A. Guantunco, P. Friedel and A. S. Giammarino, Tetrahedron (1964,20,1763) in 150 ml of methanol. The mixture was stirred for 1 hour at 0°C., 150 ml of 5% sodium hydroxide solution were added, and the mixturewas extracted with ethyl acetate. The combined organic phases werewashed with water and saturated NaCl solution, dried and concentrated.This gave 8.3 g (67% of theory) of a colorless oil which was furtheremployed directly.

1.)5-Methoxy-6-methoxymethyl-4-(2-phenyltetrahydrothiophen-4-ylamino)pyrimidine

1.6 g (8.5 mmol) of 4-chloro-5-methoxy-6-methoxymethylpyrimidine, 1.5 g(8.5 mmol) of 4-amino-2-phenyltetrahydrothiophene (prepared from2-phenyl-4-oxo-tetrahydrothiophene (cf. D. N. Reinhard, W. P.Trompenaars, I. Geevers, Synthesis 1978, 368) analogously to the routegiven in Example B) and 2 ml (14 mmol) of triethylamine were heated for24 hours at 85° C. After cooling, the mixture was diluted with water andextracted with ether, and the organic phase was washed with saturatedNaCl solution. After drying and concentrating, the residue was purifiedby column chromatography using petroleum ether/ethyl acetate (9:1). Thisgave 1.18 g (42% of theory) of a pale yellow syrup.

1.) 5-Chloro-6-ethyl-(1-allyl-2-phenylpyrrolidin-4-ylamino)pyrimidine

1.5 g (8.5 mmol) of 4,5-dichloro-6-ethylpyrimidine, 1.7 g (8.5 mmol) of1-allyl-4-amino-2-phenylpyrrolidine (prepared from1-allyl-2-phenylpyrrolidin--4-ol analogously to the route described inExample A) and 2 ml (4 mmol) of triethylamine were heated for 12 hoursat 85° C. After cooling, the mixture was diluted with water andextracted with ether, and the organic phase was washed with saturatedNaCl solution. After drying and concentrating, the residue was purifiedby column chromatography using petroleum ether/ethyl acetate (9:1, 8:2).This gave 0.95 g (33% of theory) of a colorless syrup (diastereomers1:1)

2.) Preparation of the starting material 1-allyl-2-phenylpyrrolidin-4-ol

14.7 g (128 mmol) of methanesulfonyl chloride were added dropwise at 0°C. to a solution of 16.2 g (98.2 mmol) of 1-phenyl-3-buten-1-ol epoxideand 15 g (148 mmol) of triethylamine in 130 ml of dichloromethane. Themixture was stirred for 1 hour at 0° C., 60 ml (790 mmol) of allylaminewere added, and the mixture was stirred for 10 hours at roomtemperature. The mixture was subsequently washed with saturated NaHCO₃solution, dried and concentrated, and the residue was purified by columnchromatography using petroleum ether/ethyl acetate (7:3; 1%diisopropylamine). This gave 8.2 g (41% of theory) of a colorless oil.

1.) 5-Chloro-6-ethyl-4-(1-acetyl-2-phenylpyrrolidin4-ylamino)pyrimidine

A 4-necked flask equipped with dropping funnel and distillation bridgewas charged with 3.1 g (9 mmol) of5-chloro-6-ethyl-4-(1-allyl-2-phenylpyrrolidon-4-ylamino)pyrimidine, 300mg of tris(triphenylphosphine)rhodium(I) chloride, 140 ml ofacetonitrile and 30 ml of water under a stream of N₂. The mixture washeated in such a way that the solvent mixture distilled off whilesimultaneously the same volume of the mixture was returned via thedropping funnel. After 7 hours, the mixture was cooled and diluted withdichloromethane, the phases were separated, and the organic phase waswashed with saturated NaCl solution. After the mixture had been driedand evaporated on a rotary evaporator, the residue was dissolved in 30ml of dichloromethane and treated with 1.4 g (14 mmol) of triethylamineand 1.2 g (12 mmol) of acetic anhydride. After the solution had beenstirred for 30 minutes, it was treated with water and washed withsaturated NaHCO₃ and saturated NaCl solution. The organic phase wasdried and concentrated and the residue was purified by columnchromatography using petroleum etherlethyl acetate (7:3, 1:1, 1%diisopropylamine). This gave 1.2 g (40% of theory) as a pale yellow oil(diastereomers 1:1).

1.) 5-Chloro-6-ethyl-4-(2-phenyltetrahydropyran-5-ylamino)pyrimidine

2.4 g (13.5 mmol) of 4,5-dichloro-6-ethylpyrimidine, 2.4 g (13.5 mmol)of 5-amino-2-phenyltetrahydropyran (prepared from2-phenyltetrahydropyran-5-ol (cf. U.S. Pat. No. 4,388,104) analogouslyto the routes described in Example A) and 3 ml (21 mmol) oftriethylamine were heated for 12 hours at 85° C. After cooling, themixture was diluted with water and extracted with ether, and the organicphase was washed with saturated NaCl solution. After drying andconcentrating, the residue was purified by column chromatography usingpetroleum ether/ethyl acetate (9:1, 8:2). This gave 0.65 g (15% oftheory) of the trans isomer as a colorless oil and 2.17 g (51% oftheory) of the cis isomer as a colorless oil.

The compounds of the tables which follow are obtained analogously toExamples A to F.

TABLE 1

Ex. M.p. No. R² R³ R⁴ R⁶ X Z [° C.] 1 C₂H₅ Cl H H NH O 67 2 CH₃OCH₂ OCH₃H H NH O 3 C₂H₅ Cl H CH₃ NH O Oil 4 C₂H₅ Br H CH₃ NH O Oil 5 CH₃OCH₂OCH₃ H CH₃ NH O Oil 6 C₂H₅ Cl H CH₃ O O 7 (CH)₄ H CH₃ NH O 135 8 C₂H₅ ClH CF₃ NH O 54 9 CH₃OCH₂ OCH₃ H CF₃ NH O Oil 10 C₂H₅ Cl H CF₃ O O Oil 11(CH)₄ H CF₃ O O 75 12 C₂H₅ Cl CH₃ CH₃ NH O Oil 13 CH₃OCH₂ OCH₃ CH₃ CH₃Nh O Oil 14 C₂H₅ Cl CH₃ CH₃ O O Oil 15 (CH)₄ CH₃ CH₃ O O Oil 16 C₂H₅ ClH C₂H₅ NH O Oil 17 C₂H₅ Br H C₂H₅ NH O 18 CH₃OCH₂ OCH₃ H C₂H₅ NH O Oil19 C₂H₅ Cl H C₂H₅ O O 20 (CH)₄ H C₂H₅ O O 21 C₂H₅ Cl H n-C₃H₇ NH O Oil22 C₂H₅ Br H n-C₃H₇ NH O Oil 23 CH₃OCH₂ OCH₃ H n-C₃H₇ NH O Oil 24 C₂H₅Cl H n-C₃H₇ O O Oil 25 (CH)₄ H n-C₃H₇ NH O 153 26 C₂H₅ Cl H i-C₃H₇ NH OOil 27 C₂H₅ Br H i-C₃H₇ NH O 28 CH₃OCH₂ OCH₃ H i-C₃H₇ NH O Oil 29 C₂H₅Cl H n-C₄H₉ NH O Oil 30 C₂H₅ Br H n-C₄H₉ NH O 31 CH₃OCH₂ OCH₃ H n-C₄H₉NH O Oil 32 C₂H₅ Cl H n-C₄H₉ O O Oil 33 (CH)₄ H n-C₄H₉ O O Oil 34 C₂H₅Cl H t-C₄H₉ NH O Oil 35 C₂H₅ Br H t-C₄H₉ NH O Oil 36 CH₃OCH₂ OCH₃ Ht-C₄H₉ NH O Oil 37 C₂H₅ Cl H n-C₅H₁₁ NH O Oil 38 C₂H₅ Br H n-C₅H₁₁ NH OOil 39 CH₃OCH₂ OCH₃ H n-C₅H₁₁ NH O Oil 40 C₂H₅ Cl H n-C₅H₁₁ O O Oil 41(CH)₄ H n-C₅H₁₁ O O Oil 42 C₂H₅ Cl H CH₂OCH₃ O O 43 (CH)₄ H CH₂OCH₃ O O44 C₂H₅ Cl H CH₂OCH₃ NH O Oil 45 C₂H₅ Br H CH₂OCH₃ NH O Oil 46 CH₃OCH₂OCH₃ H CH₂OCH₃ NH O Oil 47 (CH)₄ H CH₂OCH₃ NH O 48 C₂H₅ Cl H phenyl NH OOil 49 CH₃OCH₂ OCH₃ H phenyl NH O Oil 50 (CH)₄ H phenyl NH O Oil 51 C₂H₅Cl H phenyl O O Oil 52 (CH)₄ H phenyl O O Oil 53 C₂H₅ Cl CH₃ phenyl NH OOil 54 C₂H₅ Cl CH₃ phenyl O O Oil 55 (CH)₄ CH₃ phenyl O O 85 56 C₂H₅ ClH 2-methyl- NH O phenyl 57 CH₃OCH₂ OCH₃ H 2-methyl- NH O phenyl 58 C₂H₅Cl H 3-methyl- NH O phenyl 59 CH₃OCH₂ OCH₃ H 3-methyl- NH O phenyl 60C₂H₅ Cl H 4-methyl- NH O 96 phenyl 61 CH₃OCH₂ OCH₃ H 4-methyl- NH O Oilphenyl 62 C₂H₅ Cl H 4-methyl- O O Oil phenyl 63 (CH)₄ H 4-methyl- O OOil phenyl 64 C₂H₅ Cl H 3,5-di- NH O methyl- phenyl 65 C₂H₅ Cl H 3,4-di-NH O methyl- phenyl 66 C₂H₅ Cl H 4-meth- NH O Oil oxyphenyl 67 CH₃OCH₂OCH₃ H 4-meth- NH O Oil oxyphenyl 68 C₂H₅ Cl H 3-fluoro- NH O Oil phenyl69 CH₃OCH₂ OCH₃ H 3-fluoro- NH O phenyl 70 C₂H₅ Cl H 4-fluoro- NH O 73phenyl 71 CH₃OCH₂ OCH₃ H 4-fluoro- O O Oil phenyl 72 C₂H₅ Cl H 4-fluoro-O O Oil phenyl 73 (CH)₄ H 4-fluoro- O O 77 phenyl 74 C₂H₅ Cl H 3-chloro-NH O phenyl 75 CH₃OCH₂ OCH₃ H 3-chloro- NH O phenyl 76 C₂H₅ Cl H4-chloro- NH O phenyl 77 CH₃OCH₂ OCH₃ H 4-chloro- NH O phenyl 78 C₂H₅ ClH 3-bromo- NH O phenyl 79 CH₃OCH₂ OCH₃ H 3-bromo- NH O phenyl 80 C₂H₅ ClH 4-bromo- NH O Oil phenyl 81 CH₃OCH₂ OCH₃ H 4-bromo- NH O phenyl 82C₂H₅ Cl H 4-iodo- NH O phenyl 83 CH₃OCH₂ OCH₃ H 4-iodo- NH O phenyl 84C₂H₅ Cl H 3-trifluoro- NH O Oil methoxy 85 CH₃OCH₂ OCH₃ H 3-trifluoro-NH O methoxy 86 C₂H₅ Cl H 4-trifluoro- NH O Oil methoxy 87 CH₃OCH₂ OCH₃H 4-trifluoro- NH O methoxy 88 C₂H₅ Cl H 4-phenyl- NH O Oil phenyl 89C₂H₅ Cl H 4-phenoxy- NH O Oil phenyl 90 C₂H₅ Cl H 4-phen- O O Oiloxyphenyl 91 (CH)₄ H 4-phen- O O Oil oxyphenyl 92 C₂H₅ Cl H 4-nitro- NHO 102 phenyl 93 CH₃OCH₂ OCH₃ H 4-nitro- NH O phenyl 94 C₂H₅ Cl Hfuran-2-yl NH O Oil 95 C₂H₅ Cl H phenyl NH S 110- 112 96 CH₃OCH₂ OCH₃ Hphenyl NH S Oil 97 C₂H₅ Cl H 4-chloro- NH S Oil phenyl 98 C₂H₅ Cl H4-chloro- NH SO 85-86 phenyl 99 C₂H₅ Cl H 4-chloro- NH SO₂ 132- phenyl133 100 CH₃OCH₂ OCH₃ H 4-chloro- NH S Oil phenyl 101 C₂H₅ Cl H 4-meth-NH SO 121- oxyphenyl 122 102 C₂H₅ Cl H 4-meth- NH SO 92-93 oxyphenyl 103C₂H₅ Cl H 4-meth- NH SO₂ 167- oxyphenyl 169 104 CH₃OCH₂ OCH₃ H 4-meth-NH S Oil oxyphenyl

TABLE 2

Ex. No. R² R³ R⁶ R⁷ M.p. [° C.] 105 C₂H₅ Cl H CH₃ 106 C₂H₅ Cl H C₂H₅ 107C₂H₅ Cl H t-C₄H₉ 108 C₂H₅ Cl phenyl H oil 109 C₂H₅ Cl phenyl CH₃ 110C₂H₅ Cl phenyl C₂H₅ 111 C₂H₅ Cl phenyl allyl oil 112 C₂H₅ Cl phenyli-C₃H₇ oil 113 C₂H₅ Cl phenyl t-C₄H₉ oil 114 C₂H₅ Cl phenyl phenyl 43115 C₂H₅ Cl phenyl benzyl oil 116 C₂H₅ Cl phenyl formyl 113 117 C₂H₅ Clphenyl acetyl 120 118 C₂H₅ Cl phenyl benzoyl 119 C₂H₅ Cl phenyl CH₃SO₂140 120 C₂H₅ Cl phenyl CF₃SO₂ 121 C₂H₅ Cl phenyl CH₂SCH₃ 122 C₂H₅ Clphenyl CH₂OCH₃ 123 C₂H₅ Cl phenyl CON(CH₃)₂ oil 124 C₂H₅ Cl phenylCON(H)phenyl 57 125 C₂H₅ Cl phenyl COOCH₃

TABLE 3

Ex. Nr. R² R³ R⁴ R⁶ Isomer Z M.p. [° C.] 126 C₂H₅ Cl H H O oil 127CH₃OCH₂ OCH₃ H H O 128 C₂H₅ Cl H CH₃ trans O 129 C₂H₅ Cl H CH₃ cis O 130CH₃OCH₂ OCH₃ H CH₃ trans O 131 CH₃OCH₂ OCH₃ H CH₃ cis O 132 C₂H₅ Cl Ht-C₄H₉ trans O 133 C₂H₅ Cl H t-C₄H₉ cis O 134 CH₃OCH₂ OCH₃ H t-C₄H₉trans O 135 CH₃OCH₂ OCH₃ H t-C₄H₉ cis O 136 C₂H₅ Cl H phenyl trans O oil137 C₂H₅ Cl H phenyl cis O oil 138 CH₃OCH₂ OCH₃ H phenyl trans O 139CH₃OCH₂ OCH₃ H phenyl cis O 140 C₂H₅ Cl CH₃ phenyl trans O 141 C₂H₅ ClCH₃ phenyl cis O 142 C₂H₅ Cl H 3-methylphenyl trans O 143 C₂H₅ Cl H3-methylphenyl cis O 144 C₂H₅ Cl H 4-methylphenyl trans O 99 145 C₂H₅ ClH 4-methylphenyl cis O 71 146 C₂H₅ Cl H 4-methoxyphenyl trans O 147 C₂H₅Cl H 4-methoxyphenyl cis O 148 C₂H₅ Cl H 4-fluorophenyl trans O 149 C₂H₅Cl H 4-fluorophenyl cis O 150 C₂H₅ Cl H 4-chlorophenyl trans O 151 C₂H₅Cl H 4-chlorophenyl cis O 152 C₂H₅ Cl H 4-bromophenyl trans O 153 C₂H₅Cl H 4-bromophenyl cis O 154 C₂H₅ Cl H 4-trifluoromethyl trans O 155C₂H₅ Cl H 4-trifluoromethyl cis O 156 C₂H₅ Cl H 4-difluoro- trans Omethoxyphenyl 157 C₂H₅ Cl H 4-difluoro- cis O methoxyphenyl 158 C₂H₅ ClH 4-trifluoro- trans O methoxyphenyl 159 C₂H₅ Cl H 4-trifluoro- cis Omethoxyphenyl 160 C₂H₅ Cl H 4-trifluoromethyl trans O 161 C₂H₅ Cl H4-trifluoromethyl cis O 162 C₂H₅ Cl H 4-n-butylphenyl trans O 163 C₂H₅Cl H 4-n-butylphenyl cis O 164 C₂H₅ Cl H 4-t-butylphenyl trans O 165C₂H₅ Cl H 4-t-butylphenyl cis O 166 C₂H₅ Cl H dioxolan-2-yl trans O 167C₂H₅ Cl H dioxolan-2-yl cis O 168 C₂H₅ Cl H 1,3-dioxan-2-yl trans O 169C₂H₅ Cl H 1,3-dioxan-2-yl cis O 170 C₂H₅ Cl H methoxymethyl trans O 171C₂H₅ Cl H methoxymethyl cis O 172 C₂H₅ Cl H hydroxyethyl trans O 173C₂H₅ Cl H hydroxyethyl cis O 174 C₂H₅ Cl H 2-hydroxy-2- trans O propyl175 C₂H₅ Cl H 2-hydroxy-2- cis O propyl 176 C₂H₅ Cl H ethenyl trans O177 C₂H₅ Cl H ethenyl cis O 178 C₂H₅ Cl H propan-2-yl trans O 179 C₂H₅Cl H propan-2-yl cis O 180 C₂H₅ Cl H ethoxy trans O 181 C₂H₅ Cl H ethoxycis O 182 C₂H₅ Cl H 2-methyl-1- trans O propoxy 183 C₂H₅ Cl H2-methyl-1- cis O propoxy

C. Biological Examples Use as Fungicide

The activity of the preparations according to the invention was assessedusing a 0-4 scale, in which

0 means a disease suppression of 0-24%

1 means a disease suppression of 25-49%

2 means a disease suppression of 50-74%

3 means a disease suppression of 75-97%

4 means a disease suppression of 97-100%.

Example G

Barley plants cv. “Maris Otter” in the 2-leaf stage were sprayed torun-off with a solution of the compound according to the invention in amixture of 40% of acetone and 60% of water. 24 hours later, the plantswere inoculated with conidia of powdery mildew of barley (Erysiphegraminis f. sp. hordei) and kept in a controlled-environment cabinet at20° C. and a relative atmospheric humidity of 75-80%. 7 days after thetreatment, the plants were examined for symptoms of powdery mildew ofbarley. The following compounds scored 3 at 500 mg of active substance/Ispray mixture:

Compounds of Examples No. 5, 7, 36.

Example H

Tomato plants cv. “First in the Field” in the 3-4-leaf stage weresprayed to run-off with a solution of the compound according to theinvention in a mixture of 40% of acetone and 60% of water. 24 hourslater, the plants were inoculated with a spore suspension ofPhytophthora infestans (20,000 spores/ml) and kept in acontrolled-environment cabinet at 15° C., first for 2 days at a relativeatmospheric humidity of 99% and then for 4 days at a relativeatmospheric humidity of 75-80%. 6 days after the treatment, the plantswere examined for symptoms of Phytophthora infestans. The followingcompounds scored 3 or 4 at 500 mg of active substance/I spray mixture:

Compounds of Examples No. 5, 96, 103.

Example I

Grapevine seedings cv. “Grüner Veltliner” approximately 6 weeks old weresprayed to runoff with a solution of the compound according to theinvention in a mixture of 40% of acetone and 60% of water. 24 hourslater, the plants were inoculated by spraying with a Zoospore suspension(100,000/ml) of Plasmopora viticola and kept in a controlled-environmentcabinet at 70° C. and a relative atmospheric humidity of approximately99%. 14 days after the treatment, the plants were examined for symptomsof Plasmopora viticola. The following compounds scored 3 or 4 at 500 mgof active substances spray mixture:

Compounds of Examples No. 9, 10, 11, 13, 16, 22, 23, 25, 29, 31, 32, 33,34, 50, 53, 61, 67, 68, 70, 71, 80, 84, 86, 89, 113.

Example K

Wheat plants cv. “Hornet” in the 2-leaf stage were sprayed to run-offwith a solution of the compound according to the invention in a mixtureof 40% of acetone and 60% of water. 24 hours later, the plants wereinoculated by spraying with a pyknospore suspension (500,000/ml) ofLeptosphaeria nodorum and kept in a controlled-environment cabinet at18-20° C. and a relative atmospheric humidity of approximately 99%. 14days after innoculation, the plants were examined for symptoms ofLeptosphaeria nodorum.

The following compounds scored 3 or 4 at 500 mg of active substance/Ispray mixture:

Compounds of Examples No.18, 22, 23, 25, 28, 34, 36, 50, 53, 55, 63, 70,71, 73, 80, 86, 119.

Example L

Rice plants cv. “Nihonbare” in the 1.5-leaf stage were sprayed torun-off with a solution of the compound according to the invention in amixture of 40% of acetone and 60% of water. A solution of the substancein a mixture of 5% of acetone and 95% of water was appliedsimultaneously by pouring. 24 hours later, the plants were inoculated byspraying with a pyknospore suspension (10⁶/ml) of Pyricularia oryzae.The plants were kept for 2 days in a darkened controlled-environmentcabinet at 26° C. and a relative atmospheric humidity of 99% andsubsequently transferred into an illuminated controlled-environmentcabinet at approximately 18° C. and a relative atmospheric humidity of75-80%. 7-9 days afger innoculation, the plants were examined forsymptoms of Pyricularia oryzae.

The following substances scored 3 or 4 at 500 mg of active substance/Ispray mixture:

Compounds of Examples No. 1, 9, 21, 22, 23, 25, 26, 31, 34, 36, 37, 38,48, 49, 53, 70, 86, 90, 91, 111.

Example M

Apple seedlings (Malus sp.) approximately 3 weeks old were sprayed torunoff with a solution of the compound according to the invention in amixture of 40% of acetone and 60% of water. After 24 hours, the plantswere inoculated by spraying with a spore suspension (300,000/mi) ofVenturia inaequalis. The plants were kept for 2 days in the dark at18-20° C. and a relative atmospheric humidity of 99%, subsequently inthe light for 5 days at the same atmospheric humidity and finally for 7days at an atmospheric humidity of 75-80%. 14 days after the treatment,the plants were examined for symptoms of Venturia inaequalis.

The following substances scored 3 or 4 at 500 mg of active substance/Iof spray mixture:

Compounds according to Examples No. 21, 23, 36.

Example N

Tomato plants cv. “First in the Field” in the 2-3-leaf stage weresprayed to run-off with a solution of the compound according to theinvention in a mixture of 40% of acetone and 60% of water. After 24hours, the plants were inoculated with a spore suspension (500,000/ml)of Botrytis cinerea. The plants were kept in a conrolled-environmentcabinet at 18-20° C. and a relative atmospheric humidity of 99%. 5 daysafter innoculation, the plants were examined for symptoms of Botrytiscinerea. The following substances scored 3 or 4 at 500 mg of activesubstance/I spray mixture:

Compounds of Examples No. 23, 71, 84, 99.

Use as Insecticide/acaricide Example O

Portions of 1 ml of the test formulation, emulsified in water, wereapplied uniformly to the insides of the dish and of the cover of a Petridish and, after the coating had dried on, batches of 10 imagines of thecommon housefly (Musca domestica) were introduced. After the dishes hadbeen closed, they were kept at room temperature, and the mortality ofthe test animals was determined after 3 hours. At 300 ppm (activesubstance content in the test solution), the preparations of ExamplesNo.3, 4, 21, 22, 23, 34, 35, 36, 48, 49, 60, 61, 68, 71, 80, 86, 137showed 100% mortality of the test animals which had been introduced.

Example P

Rice seed was germinated on cotton wool in glass culture dishes undermoist conditions and after they had grown to a stem length ofapproximately 8 cm, the leaves were introduced into the test solution.After the solution had run off, the treated rice plants were introducedinto culture containers separately for each test concentration andpopulated with batches of 10 larvae (L3) of the species Nilaparvatalugens. After the sealed culture containers had been kept at 21° C., themortality of the leafhopper larvae was determind after 4 days. At aconcentration of 300 ppm (active substance content in the testsolution), 100% mortality of the test animals introduced was shown bythe preparations of Examples No. 8, 9, 21, 22, 23, 38, 48, 49, 50, 60,71, 80, 84, 86, 42, 137.

Example Q

Wheat seed was pregerminated for 6 hours under water and thentransferred into 10 ml glass test tubes and covered with 2 ml of soil ineach case. After 1 ml of water had been added, the plants remained inthe culture tubes at room temperature (21° C.) until they had reached aplant height of approximately 3 cm. Diabrotical undecimpunctata larvaein the middle stage (batches of 10) were subsequently introduced ontothe soil in the glass tubes and, after 2 hours, 1 ml of the test liquidin the concentration to be tested was pipefted onto the soil surface inthe glass tubes. After they had been left to stand for 5 days underlaboratory conditions (21° C.), soil and roots were examined for liveDiabrotica larvae and the mortality was determined. At 300 ppm (activesubstance content in the test solution), 100% mortality of the testanimals which had been introduced was shown by the preparations ofExamples No.3, 4, 8, 9, 11, 16, 18, 21, 22, 23, 26, 29, 33, 34, 35, 36,37, 38, 39, 41, 48, 49, 50, 53, 68, 70, 80, 84, 86, 94, 96, 97, 98, 100,104, 111, 137.

Example R

Field beans (Vicia faba) which were severely populated with the blackbean aphid (Aphis fabae) were sprayed with aqueous dilutions of wettablepowder concentrates with an active substance content of 300 ppm to thestage of beginning run-off. The mortality of the aphids was determinedafter 3 days. A 100% destruction was achieved with the compounds ofExamples No. 21, 22, 23, 26, 27, 29, 37, 38, 60, 61, 67, 68, 70, 71, 80,84, 86, 137.

Example S

Bean plants (Phaseolus v.) which were severely infested with greenhousered spider mites (Tetranychus urticae, full population) were sprayedwith the aqueous dilution of a wettable powder concentrate whichcontained 300 ppm of the active substance in question. The mortality ofthe mites was checked after 7 days. 100% destruction was achieved withthe compounds of Examples No. 9, 48, 49, 61, 66, 67, 68, 70, 71, 80, 86,89, 137.

Use as Ovicide Example T

Filter paper disks supporting eggs of the large milkweed bug (Oncopeltusfasciatus) were each treated with 0.5 ml portions of aqueous dilution ofthe test formulation. After the coating had dried on, the Petri dish wasclosed and the inside was kept at maximum atmospheric humidity. Afterthe dishes had been kept at room temperature, the ovicidal activity wasdetermined after 7 days. At an active substance content of 300 ppm, 100%ovicidal activity was achieved by the compounds of Examples No. 3, 4,21, 22, 23, 34, 36, 48, 49, 90, 60, 61, 68, 70, 71, 80, 86, 92, 100,137.

Use as antiparasitic Example U

In-vitro test on tropical cattle ticks (Boophilus microplus)

The activity of the compounds according to the invention against tickswas demonstrated in the following experimental set-up:

To produce a suitable preparation of active substance, the activesubstances were dissolved at a concentration of 10% (w/v) in a mixturecomposed of dimethylformamide (85 g), nonylphenyl polyglycol ether (3 g)and oxyethylated castor oil (7 g) and the resulting emulsionconcentrates were diluted with water to a test concentration of 500 ppm.

Batches of ten female tropical ticks, Boophilus microplus, which hadsucked themselves full were immersed for five minutes in these dilutionsof active substance. The ticks were subsequently dried on filter paperand then attached, with 25 their backs, to an adhesive film in order todeposit eggs. The ticks were kept in an incubator at 28° C. and anatmospheric humidity of 90%. For the control, female ticks were immersedin water only. The activity was assessed on the basis of the inhibitionof egg deposition two weeks after the treatment.

In this test, the compounds of examples no. 21, 34, 37, 38, 39, 70, 86caused in each case 100% inhibition of deposition.

What is claimed is:
 1. A compound of the formula I

in which R¹ is hydrogen, fluorine or chlorine R² and R³ independently ofone another are hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,(C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl, (C₂-C₄)-alkynyl,(C₂-C₄)-haloalkynyl, tri-(C₁-C₄)-alkylsilyl-(C₂-C₄)-alkynyl,(C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,(C₁-C₄)-haloalkoxy-(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-haloalkyl,(C₁-C₄)-haloalkoxy-(C₁-C₄)-haloalkyl, halogen, hydroxyl,(C₁-C₄)-hydroxyalkyl, (C₁-C₄)-alkanoyl, (C₁-C₄)-alkanoyl-(C₁-C₄)-alkyl,(C₂-C₄)-haloalkanoyl, (C₃-C₅)-cycloalkyl, (C₃-C₅)-halocycloalkyl,(C₄-C₅)-cycloalkenyl, (C₄-C₅)-halocycloalkenyl, (C₃-C₅)-cycloalkoxy,cyano, cyan-(C₁-C₄)-alkyl, nitro, nitro-(C₁-C₄)-alkyl, thiocyano,thiocyano-(C₁-C₄)-alkyl, (C₁-C₄)-alkoxycarbonyl,(C₁-C₄)-alkoxycarbonyl-(C₁-C₄)-alkyl, (C₁-C₄)-haloalkoxycarbonyl,(C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,(C₁-C₄)-alkylthio-(C₁-C₄)-alkyl, (C₁-C₄)-haloalkylthio-(C₁-C₄)-alkyl,(C₁-C₄)alkylthio-(C₁-C₄)-haloalkyl, (C₁-C₄)-alkylsulfmyl,(C₁-C₄)-haloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl,(C₁-C₄)-haloalkylsulfonyl; or R² and R³ together with the carbon atomsto which they are bonded form an unsaturated 5- or 6-member carbocyclicring which, it is a 5-membered ring, a CH₂ is optionally replaced by anoxygen or sulfur atom or which, if it is a 6-membered ring, one or twoCH units is optionally replaced by a nitrogen atom, and which isoptionally substituted by 1, 2 or 3 identical or different radicals andthese radicals are (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, halogen,(C₁-C₄)-alkoxy or (C₁-C₄)-haloalkoxy; or R² and R³ together with thecarbon atoms to which they are bonded form a saturated 5-, 6- or 7-membered carbocyclic ring in which on CH₂-group is optionally replacedby oxygen or sulfur and which is optionally substituted by 1, 2 or 3(C₁-C₄)-alkyl groups; A is N; X is NH, oxygen or S(O)_(q) where q=0, 1or 2; Y is a direct bond or CH₂; Z is oxygen or sulfur; R⁴, R⁵ and W-R⁶are substituents of the heteroaliphatic ring system, where R⁴ and R⁵independently of one another are hydrogen, halogen, cyano,(C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl,(C₂-C₄)-alkynyl, (C₂-C₄)-haloalkynyl, (C₃-C₆)-cycloalkyl,(C₄-C₆)-Cycloalkenyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy,(C₁-C₄)-alkanoyloxy, (C₁-C₄)-haloalkanoyloxy, (C₁-C₄)-alkylthio or(C₁-C₄)-haloalkylthio; W is a direct bond, oxygen, —NR¹², —CO—, —COO—,CONR¹²—, sulfur, —C═N—, —C═N—O— or —NR¹²O—; R⁶ is alkyl, alkenyl,alkynyl, cycloalkyl or cycloalkenyl wherein the last-mentioned 5radicals are optionally substituted by one or more, in the case offluorine up to the maximum number of, identical or different radicalsD¹R¹⁶, or R⁶ is aryl which is unsubstituted or substituted by up tothree, in the case of fluorine also up to the maximum number of,identical or different radicals D²R¹⁷, or R⁴ and R⁶ together form athree- to eight-membered ring system which is linked spirocyclically tothe ring system containing Y and Z and in which one CH₂ group in thering formed by R⁴ and R⁶ is optionally replaced by hetero atom unitsselected from the group consisting of oxygen, S(O)_(n) where n=0, 1 or2, or NR¹⁸ where R¹² is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkanoyl or(C₃-C₅)-cycloalkyl; R¹⁸ is hydrogen, alkyl, alkanoyl, alkoxy, benzyl, oraryl, wherein the last-mentioned 2 radicals are unsubstitutedsubstituted with up to three, in the case of fluorine also up to themaximum number of, identical or different substituents R¹⁹; R¹⁹ is(C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy,cyano, nitro or halogen, and the ring system formed by R⁴ and R⁶ isunsubstituted or substituted with up to three substituents D³R²⁰, or thering system formed by R⁴ and R⁶ together with a fither benzene ring orcyclohexane ring forms a fused ring system and the benzene ring in thesefused systems are unsubstituted or substituted with up to three, in thecase of fluorine also up to the maximum number of, identical ordifferent substituents D⁴R²¹, where D¹, D², D³ and D⁴ are in each caseindependent of one another and are a direct bond, oxygen, S(O)_(k),SO₂O, OSO₂, CO, OCO, COO, SO₂NR²², NR²²SO₂, NR²²O, ONR²², NR²², NR²²CO,CONR²² or SiR²³R²⁴, where k is 0, 1 or 2; and R¹⁶, R¹⁷, R²⁰ and R²¹ ineach case independently of one another are hydrogen, cyano, nitro,halogen, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl, (C₂-C₈)-alkenyl,(C₂-C₈)-haloalkenyl, (C₂-C₈)alkynyl, (C₂-C₈)-haloalkynyl,(C₁-C₈)-alkoxy(C₁-C₄)-alkyl, (C₁-C₈)-haloalkoxy(C₁-C₄)-alkyl,(C₁-C₈)-alkylthio(C₁-C₄)-alkyl, (C₁-C₈)-haloalkylthio (C₁-C₄)-alkyl,(C₃-C₈)-cycloalkyl, (C₄-C₈)-cycloalkenyl,(C₃-C₈)-cycloalkyl-(C₁-C₄)-alkyl, (C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkyl,aryl or aryl-(C₁-C₄)-alkyl wherein the cycloaliphatic or aromatic ringsystems in the last-mentioned 6 radicals are unsubstituted orsubstituted with up to three, in the case of fluorine also up to themaximum number of, identical or different substituents R²⁵, where R²²radicals independently of one another are hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkanoyl or (C₃-C₅)-cycloalkyl and R²³ and R²⁴ independently ofone another are (C₁-C₄)-alkyl and R²⁵ radicals independently of oneanother are (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkoxy, cyano, nitro, halogen, (C₁-C₄)-alkanoyl or(C₂-C₄)-haloalkanoyl, or two of the radicals R¹⁶, R¹⁷, R²⁰, R²¹, R²⁵ onthe same carbon atom together and in each case independently of oneanother are an oxo group; or a salt thereof.
 2. A compound of theformula I as claimed in claim 1 where R² and R³ independently of oneanother are hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₂-C₄)-alkenyl,(C₂-C₄)-haloalkenyl, (C₂-C₄)-alkynyl, (C₂-C₄)-haloalkynyl,tri-(C₁-C₄)-alkylsilyl-(C₂-C₄)-alkynyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,(C₁-C₄)haloalkoxy-(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-haloalkyl,(C₁-C₄)-haloalkoxy-(C₁-C₄)-haloalkyl, halogen, hydroxyl,(C₁-C₄)-hydroxyalkyl, (C₁-C₄)-alkanoyl, (C₁-C₄)-alkanoyl-(C₁-C₄)-alkyl,(C₂-C₄)-haloalkanoyl, (C₃-C₅)-cycloalkyl, (C₃-C₅)-halocycloalkyl,(C₄-C₅)-cycloalkenyl, (C₄-C₅)-halocycloalkenyl, (C₃-C₅)-cycloalkoxy,cyano, cyan-(C₁-C₄)-alkyl, nitro, nitro-(C₁-C₄)-alkyl, thiocyano,thiocyano-(C₁-C₄)-alkyl, (C₁-C₄)-alkoxycarbonyl,(c₁-C₄)alkoxycarbonyl-(C₁-C₄)-alkyl, (C₁-C₄)-haloalkoxycarbonyl,(C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,(C₁-C₄)-alkylthio-(C₁-C₄)-alkyl, (C₁-C₄)haloalkylthio-(C₁-C₄)-alkyl,(C₁-C₄)-alkylthio-(C₁-C₄)-haloalkyl, (C₁-C₄)-alkylsulfinyl,(C₁-C₄)-haloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl,(C₁-C₄)-haloalkylsulfonyl; or R² and R³ together with the carbon atomsto which they are bonded form an unsaturated 5- or 6-memberedcarbocyclic ring which, if it is a 5-membered ring, one or two CH₂ unitsare optionally replaced by one or two nitrogen atoms, and which isoptionally substituted by 1, 2 or 3 identical or different radicals andthese radicals are (C₁-C₄)-alkyl, trifluoromethyl, halogen,(C₁-C₄)-alkoxy or (C₁-C₄)-haloalkoxy; or R² and R³ together with thecarbon atoms to which they are bonded form a saturated 5-, 6- or7-membered carbocyclic ring in which one CH₂ is optionally replaced byan oxygen or sulfur atom, and which is optionally substituted by 1, 2 or3 (C₁-C₄)-alkyl groups; R⁴, R⁵ and W-R⁶ are substituents of theheteroaliphatic ring system, where R⁴ and R⁵ independently of oneanother are hydrogen, halogen, cyano, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,(C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl, (C₂-C₄)-alkynyl,(C₂-C₄)-haloalkynyl, (C₃-C₆)-cycloalkyl, (C₄-C₆)-cycloalkenyl,(C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkanoyloxy,(C₁-C₄)-haloalkanoyloxy, (C₁-C₄)-alkylthio or (C₁-C₄)-haloalkylthio; Wis a direct bond, oxygen, —NR¹²—, —CO—, —COO—, CONR¹²—, sulflur, —C═N—,—C═N—O— or —NR¹²O—; R⁶ is alkyl, alkenyl, alkynyl, cycloalkyl orcycloalkenyl and wherein these last-mentioned 5 radicals are optionallysubstituted by up to three, in the case of fluorine up to the maximumnumber of, identical or different radicals D¹R¹⁶, or R⁶ is aryl which isunsubstituted or substituted by up to three, in the case of fluorinealso up to the maximum number of, identical or different radicals D²R¹⁷,or R⁴ and R⁶ together form a three- to eight-membered ring system whichis linked spirocyclically to the ring system containing Y and Z and inwhich one CH₂ group in the ring formed by R⁴ and R⁶ is optionallyreplaced by hetero atom units selected from the group consisting ofoxygen, S(O)_(n) where n=0, 1 or 2, or NR¹⁸, where R¹² is hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkanoyl or (C₃-C₅)-cycloalkyl; R¹⁸ is hydrogen,alkyl, alkanoyl, alkoxy, benzyl, or aryl wherein the last-mentioned 2radicals are unsubstituted or substituted with up to three, in the caseof fluorine also up to the maximum number of, identical or differentsubstituents R¹⁹, R¹⁹ is (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,(C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, cyano, nitro or halogen, and thering system formed by R⁴ and R⁶ can be unsubstituted or provided withone substituent, D³R³, or the ring system formed by R⁴ and R⁶ togetherwith a further benzene ring or cyclohexane ring forms the indane,1,2,3,4-tetrahydronaphthalene, decalin or benzocycloheptane system, andthe benzene ring in these fised systems is unsubstituted or substitutedwith up to three, in the case of fluorine also up to the maximwn numberof, identical or different substituents D⁴R²¹, where D¹, D², D³ and D⁴are in each case independent of one another and are a direct bond,oxygen, S(O)_(k), SO₂O, OSO₂, CO, OCO, COO, SO₂NR²², NR²²SO₂, NR²²O,ONR²², NR²², NR²²CO, CONR²² or SiR²³R²⁴, where k is 0, 1 or 2; and R¹⁶,R¹⁷, R²⁰ and R²¹ in each case independently of one another are hydrogen,cyano, nitro, halogen, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl,(C₂-C₈)-alkenyl, (C₂-C₈)-haloalkenyl, (C₂-C₈)alkynyl,(C₂-C₈)-haloalkynyl, (C₁-C₈)-alkoxy(C₁-C₄)-alkyl,(C₁-C₈)-haloalkoxy(C₁-C₄)-alkyl, (C₁-C₈)-alkylthio(C₁-C₄)-alkyl,(C₁-C₈)-haloalkylthio (C₁-C₄)-alkyl, (C₃-C₈)-cycloalkyl,(C₄-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkyl-(C₁-C₄)-alkyl,(C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkyl, aryl, or aryl-(C₁-C₄)-alkyl whereinthe cycloaliphatic or aromatic ring systems in the last-mentioned 6radicals are unsubstituted or substituted with up to three, in the caseof fluorine also up to the maximum number of, identical or differentsubstituents R²⁵, where R²² radicals independently of one another arehydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkanoyl or (C₃-C₅)-cycloalkyl and R²³and R²⁴ independently of one another are (C₁-C₄)-alkyl and R²⁵ radicalsindependently of one another are (C₁-C₄)-aIkyl, (C₁-C₄)-haloalkyl,(C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, cyano, nitro, halogen,(C₁-C₄)-alkanoyl or (C₂-C₄)-haloalkanoyl, or two of the radicals R¹⁶,R¹⁷, R²⁰, R²¹, R²⁵ on the same carbon atom together and in each caseindependently of one another are an oxo group or an acid addition saltthereof.
 3. A compound of the formula I as claimed in claim 1 where R¹is hydrogen, chlorine or fluorine, R² is (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl,(C₂-C₄)-alkynyl, tri-(C₁-C₄)-alkylsilyl-(C₂-C₄)-alkynyl,(C₁-C₄)-haloalkyl, cyclopropyl, halocyclopropyl, methoxymethyl or cyano;R³ is hydrogen, halogen, methyl, ethyl, ethenyl, ethynyl, methoxy,ethoxy, cyano, trifluoromethyl, fluoromethylthio or methoxycarbonyl; orR² and R³ together with the carbon atoms to which they are bonded forman unsaturated 5- or 6-membered carbocyclic ring which, if it is a5-membered ring, a CH₂, is optionally replaced by a sulfur atom andwhich is optionally substituted by 1, 2, or 3 identical or differentradicals and these radicals are (C₁-C₄)-alkoxy or (C₁-C₄)-haloalkoxy; orR² and R³ together with the carbon atoms to which they are bonded form asaturated 5- or 6-membered ring in which one CH group is optionallyreplaced by sulfur; A is N; X is NH or oxygen; Y is a direct bond orCH₂; Z is oxygen or sulfur; R⁴ is hydrogen, (C₁-C₄)-alkyl,trifluoromethyl or (C₁-C₄)-alkoxy; R⁵ is hydrogen; and W is a directbond, oxygen, —CO—, —COO—, CONR¹², sulfur, —C═N—, —C═N—O— and R¹² ishydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkanoyl or (C₃-C₅)-cycloalkyl.
 4. Acompound of the formula I as claimed in claim 1 where R¹ is hydrogen, R²is methyl, ethyl, propyl, isopropyl, (C₁-C₂)-fluoroalkyl, cyclopropyl ormethoxymethyl; R³ is halogen, methyl, ethyl, ethenyl, ethynyl, methoxy,ethoxy, trifluoromethyl, fluoromethylthio, methoxycarbonyl or cyano; orR² and R³ together with the ring system to which they are bonded formthe quinazoline system which is optionally substituted by fluorine inthe carbocyclic moiety; or R² and R³ together with the carbon atoms towhich they are bonded form a saturated 6-membered ring in which one CH₂group is optionally replaced by an oxygen or sulfur atom; R⁴ is hydrogenor methyl; and R⁵ is hydrogen.
 5. An insecticidal composition comprisingan insecticidally active amount of one or more of a compound as claimedin claim 1 together with one or more of an additive or auxiliary.
 6. Acompound of the formula I as claimed in claim 1 where R⁶ is(C₁-C₂₀)-alkyl, (C₂-C₂₀)-alkenyl, (C₂-C₂₀)-alkynyl, (C₃-C₈)-cycloalkylor (C₄-C₈)-cycloalkenyl, and where these last-mentioned 5 radicals, canoptionally be substituted by up to three, in the case of fluorine up tothe maximum number of, identical or different radicals D¹R¹⁶, or R⁶ isaryl which is unsubstituted or substituted by up to three, in the caseof fluorine also up to the maximum number of, identical or differentradicals D²R¹⁷, or R⁴ and R⁶ together form a three- to eight-memberedring system which is spirocyclically linked with the ring systemcontaining Y and Z and in which one CH₂ group in the ring formed by R⁴and R⁶ is optionally replaced by hetero atom units selected from thegroup consisting of oxygen, S(O)_(n) where n=0, 1 or 2 or NR¹⁸, R¹⁸ ishydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-alkanoyl, (C₁-C₈)-alkoxy, benzoyl, oraryl, wherein the last-mentioned 2 radicals to be unsubstituted orsubstituted with up to three, in the case of fluorine also up to themaximum number of, identical or different substituents R¹⁹; R¹⁹ is(C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy,cyano, nitro or halogen, and the ring system formed by R⁴ and R⁶ can beunsubstituted or provided with one substituent, D³R²⁰, or the ringsystem formed by R⁴ and R⁶ together with a further benzene ring orcyclohexane ring forms the indane, 1,2,3,4-tetrahydronaphthalene,decalin or benzocycloheptane system, and the benzene ring in these fusedsystems is unsubstituted or substituted with up to three, in the case offluorine also up to the maximum number of, identical or differentsubstituents D⁴R²¹, where, amongst the compounds for which the carbonatom between Y and Z only has attached to it the substituent W-R⁶, thesubstituents X and W-R⁶ are in the cis-position relative to each other;D¹, D², D³ and D⁴ are in each case independent of one another and are adirect bond, oxygen, S(O)_(k), SO₂O, OSO₂, CO, OCO, COO, SO₂NR²²,NR²²SO₂, ONR²², NR²²O, SiR²³O, NR²²CO, CONR²² or SiR²³R²⁴, where k is 0,1 or 2; and R¹⁶, R¹⁷, R²⁰ and R²¹ in each case independently of oneanother are hydrogen, cyano, nitro, halogen, (C₁-C₈)-alkyl,(C₁-C₈)-haloalkyl, (C₂-C₈)-alkenyl, (C₂-C₈)-haloalkenyl, (C₂-C₈)alkynyl,(C₂-C₈)-haloalkynyl, (C₁-C₈)-alkoxy(C₁-C₄)-alkyl,(C₁-C₈)-haloalkoxy(C₁-C₄)-alkyl, (C₁-C₈)-alkylthio(C₁-C₄)-alkyl,(C₁-C₈)-haloalkylthio(C₁-C₄)-alkyl, (C₃-C₈)-cycloalkyl,(C₄-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkyl-(C₁-C₄)-alkyl,(C₄-C₈)-cycloalkenyl-(C₁-C₄)-alkyl, aryl or aryl-(C₁-C₄)-alkyl whereinthe cycloaliphatic, aromatic or heterocyclic ring systems in thelast-mentioned 6 radicals are unsubstituted or substituted with up tothree, in the case of fluorine also up to the maximum number of,identical or different substituents R²⁵; R²² radicals independently ofone another are hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkanoyl or(C₃-C₅)-cycloalkyl and R²³ and R²⁴ independently of one another are(C₁-C₄)-alkyl and R²⁵ radicals independently of one another are(C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy,cyano, nitro, halogen, (C₁-C₄)-alkanoyl or (C₂-C₄)-haloalkanoyl, or twoof the radicals R¹⁶, R¹⁷, R²⁰, R²¹, R²⁵ on the same carbon atom togetherand in each case independently of one another are an oxo group.
 7. Acompound of the formula I as claimed in claim 1 where R⁶ is(C₁-C₈)-alkyl, (C₂-C₈)-alkenyl, (C₂-C₈)-alkynyl, (C₃-C₈)-cycloalkyl or(C₄-C₈)-cycloalkenyl and where these last mentioned 5 radicalsoptionally is substituted by up to three, in the case of fluorine up tothe maximum number of, identical or different radicals D¹R¹⁶, or R⁶ isaryl which is unsubstituted or substituted by up to three, in the caseof fluorine also up to the maximum number of identical or differentradicals D²R¹⁷, or R⁴ and R⁶ together form a five- or six-membered ringsystem which is spirocyclically linked to the ring system containing Yand Z and in which one CH₂ group in the ring formed by R⁴ and R⁶ isoptionally replaced by hetero atom units selected from the groupconsisting of oxygen, S(O)_(n) where n=0, 1 or 2 or NR¹⁸, where R¹⁸ ishydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-alkanoyl, alkoxy, benzoyl, or arylwherein the last-mentioned 2 radicals are unsubstituted or substitutedwith up to three, in the case of fluorine also up to the maximum numberof, identical or different substituents R¹⁹, and R¹⁹ is (C₁-C₄)-alkyl,(C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, cyano, nitro orhalogen, and the ring system formed by R⁴ and R⁶ can be unsubstituted orprovided with one substituent, D³R²⁰, or the ring system formed by R⁴and R⁶ together with a further benzene ring or cyclohexane ring formsthe indane, 1,2,3,4-tetrahydronaphthalene, decalin or benzocycloheptanesystem, and the benzene ring in these fised systems is unsubstituted orprovided with up to three, in the case of fluorine also up to themaximum number of, identical or different substituents D⁴R²¹, where,amongst the compounds for which the carbon atom between Y and Z whereY=CH₂ only has attached to it the substituent W-R⁶, the substituents Xand W-R⁶ are in the cis-position relative to each other; D¹, D², D³ andD⁴ are in each case independent of one another and are a direct bond,oxygen, S(O)_(k), SO₂O, OSO₂, CO, OCO, COO, SO₂NR²², NR²²SO₂, NR²²O,ONR²², NR²², NR²²CO or CONR²², where k is 0, 1 or 2; and R²² radicalsindependently of one another are hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkanoyl or (C₃-C₅)-cycloalkyl, and where R¹⁶, R¹⁷, R²⁰ and R²¹in each case independently of one another are hydrogen, cyano, nitro,halogen, (C₁-C₈)-alkyl, (C₃-C₈)-cycloalkyl, or aryl, where thecycloaliphatic or aromatic in the last-mentioned 2 radicals areunsubstituted or substituted with up to three, in the case of fluorinealso up to the maximum number of, identical or different substitutentsR²⁵, where R²⁵ radicals independently of one another are (C₁-C₄)-alkyl,(C₁-C₄)haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, cyano, nitro,halogen, or two of the radicals R¹⁶, R¹⁷, R²⁰, R²¹, and R²⁵ on the samecarbon atom together and in each case independently of one another arean oxo group.
 8. A compound of the formula I as claimed in claim 1 whereR⁶ is (C₁-C₈)-alkyl is optionally substituted by up to three, in thecase of fluorine up to the maximum number of, identical or differentradicals D¹R²⁰, or R⁶ is aryl which is unsubstituted or to besubstituted by up to three, in the case of fluorine also up to themaximum number of, identical or different radicals D²R²¹.
 9. A compoundof the formula I as claimed in claim 1 where R¹ is hydrogen; R² isethyl, propyl, isopropyl, 1-fluoroethyl or methoxymethyl; R³ isfluorine, chlorine, bromine, cyano, ethenyl, ethynyl or methoxy; or, R²and R³ together with the ring system to which they are bonded form thequinazoline system which can be substituted by a fluorine atom; R⁴ ishydrogen or methyl; and R⁵ is hydrogen.
 10. A compound of the formula Ias claimed in claim 1 where R¹ is hydrogen; R² is ethyl ormethoxymethyl; R³ is fluorine, chlorine, bromine or methoxy; or X is NH;Z is oxygen and R⁴ and R⁵ are hydrogen.
 11. A method for controllinginsects or their eggs, which comprises applying to said insects or theireggs or to plants, areas or substrates infested with them, aninsecticidally active amount of a compound as claimed in claim 1.